Coated glass components

Abstract

This article discloses a specific coated glass element and its specific production method.

Description

Technical Field

[0001] This invention relates to a coated glass element and its manufacturing method. Background Technology

[0002] Pharmaceutical containers, such as vials or syringes, are commonly used to store pharmaceutical compositions. Furthermore, pharmaceutical compositions administered by injection typically contain a drug substance dissolved in water. If a pharmaceutical container is used for long-term storage of a composition, the interaction between the pharmaceutical composition and the container can affect the storage capacity of the pharmaceutical composition. Glass is advantageous as a material for pharmaceutical containers because, for example, it has very low gas permeability. To improve the resistance of glass surfaces, it is well known to apply coatings, such as those described in EP 0 821 079 A1 and EP 0 811 367 A2.

[0003] However, the stability of the coating, especially at high pH values, is problematic, particularly under harsh conditions or if the drug container is used to store highly sensitive drug substances, such as biological products, in alkaline buffer solutions. Summary of the Invention

[0004] The inventors recognize this problem and the purpose of this application is to provide a coating that:

[0005] It exhibits excellent tolerance over a wide pH range; and / or

[0006] It exhibits enhanced tolerance at high pH values; and / or

[0007] It has high chemical stability; and / or

[0008] It exhibits excellent adhesion properties; and / or

[0009] It has excellent air venting performance.

[0010] This problem is addressed by the specific methods and / or specific (filled) coated glass elements and / or specific applications described herein. Examples and preferred embodiments are described below. Combinations of two or more preferred embodiments are particularly preferred.

[0011] method

[0012] According to the present invention, a method for coating a glass element includes the following steps:

[0013] Provide glass components including glass surfaces; and

[0014] A coating process is performed on at least a portion of the glass surface, comprising the following steps:

[0015] The precursor P1 surrounds at least a portion of the glass surface of the glass element; and

[0016] Precursor P1 is irradiated to generate plasma;

[0017] The following parameters must be satisfied, preferably both:

[0018] The process temperature PT1 is above 200℃; and / or

[0019] ii) The irradiation pulse duration PD1 is less than 50 µs.

[0020] Preferably, the coating process is a chemical vapor deposition process. More preferably, the coating process is a plasma-enhanced chemical vapor deposition (PECVD) process, a plasma-pulsed chemical vapor deposition (PICVD) process, or a plasma-assisted chemical vapor deposition (PACVD) process, and even more preferably, a plasma-pulsed chemical vapor deposition (PICVD) process. In particular, if the process is a plasma-pulsed chemical vapor deposition (PICVD) process, the process temperature and pulse duration of the microwave plasma can be advantageously controlled. If the process is a plasma-pulsed chemical vapor deposition process and the process temperature and pulse duration of the microwave plasma are within the ranges described herein, the resilience and stability of the layer can be further improved.

[0021] The process temperature can be above 200°C. Preferably, the process temperature PT1 is from 200°C to the Tg of the glass in the glass element, more preferably from 200°C to 500°C, more preferably from 220°C to 450°C, even more preferably from 240°C to 320°C, and even more preferably from 250°C to 300°C. If the temperature is above 200°C, preferably above 220°C, the energy is sufficient to split the precursor and form a homogeneous layer. This improves the layer's resilience and stability. However, if the temperature is too high, the precursor may completely decompose. Therefore, if the temperature is from 200°C to 500°C, preferably from 250°C to 300°C, the adhesion, resilience, and stability of the layer can be further improved.

[0022] According to the present invention, the pulse duration of the microwave plasma can be 50 μs or less. Preferably, the plasma pulse duration PD1 is 50 μs or less, more preferably 40 μs or less, more preferably 30 μs or less, more preferably 20 μs or less, more preferably 15 μs or less, more preferably 12 μs or less, more preferably 8 μs or less, more preferably 6 μs or less, more preferably 4 μs or less, more preferably 3 μs or less; and / or the plasma pulse duration PD1 is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, more preferably 6 μs or more. If the pulse duration is 50 μs or less, the precursor decomposes appropriately and the resilience and stability of the layer are further increased. Therefore, if the pulse duration is 2 to 15 μs, preferably 3 to 8 μs, the resilience and stability of the layer composition can be further improved. A combination of a specific pulse duration PD1 and a specific temperature PT1 is particularly preferred.

[0023] There are no particular restrictions on the ignition method of the plasma. Preferably, irradiation is performed by a microwave generator, preferably wherein the radiation has a frequency of 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably about 2.45 GHz. Therefore, the performance of the layer can be further improved.

[0024] There are no particular limitations on the input power. Preferably, the input power IP1 of the irradiation generator, especially the input power IP1 of the microwave generator used for microwave irradiation, is 1000W to 10000W, more preferably 2100W to 8000W, more preferably 2500W to 6700W, more preferably 3000W to 6000W, more preferably 3200W to 5500W, and even more preferably 4000W to 5000W. Therefore, a homogeneous layer is ensured, and thus, the tolerance and stability of the layer composition can be further improved. A combination of a specific pulse duration PD1, a specific input power IP1, and a specific temperature PT1 is particularly preferred.

[0025] Precursor P1 is not particularly limited. Preferably, precursor P1 includes one or more and / or combinations of hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), tetramethylsilane (TMS), trimethylborazole (TMB), tris(dimethylaminosilyl)-amino-di(dimethylamino)borane (TDADB), tris(trimethylsilyl)boronic acid ester (TMSB), hexamethylcyclotrisiloxane (HMCTSO), octamethylcyclotetrasiloxane (OMCTS), decamethylcyclopentasiloxane (DMCPS), dodecylcyclohexasiloxane (DMCHS), diacetoxyditert-butoxysilane (DADBS), tetraethoxysilane (TEOS), tris(trimethylsiloxy)vinylsilane (TTMSVS), and vinyltriethoxysilane (VTES), preferably precursor P1 is HMDSO; and / or precursor P1 contains elements Si, C, O, and H, preferably composed of elements Si, C, O, and H. In particular, if the glass element is a pharmaceutical glass container, HMDSO is preferred as the precursor P1.

[0026] In one embodiment, the precursor P1 comprises a siloxane of the formula R1R2R3-Si-O-Si-R4R5R6, wherein R1, R2, R3, R4, R5 and R6 can be selected independently of each other, and wherein R1, R2, R3, R4, R5 and R6 can be selected from methyl, ethyl or propyl.

[0027] In one embodiment, precursor P1 comprises a linear siloxane selected from the list of hexamethyldisiloxane (HMDSO), octamethyltrisiloxane, decamethyltetrasiloxane, dodecylpentasiloxane, and tetradecylhexasiloxane.

[0028] In one embodiment, precursor P1 comprises a cyclic siloxane selected from the list of hexamethylcyclotrisiloxane (HMCTSO), octamethylcyclotetrasiloxane (OMCTS), decamethylcyclopentasiloxane (DMCPS), and dodecylcyclohexasiloxane (DMCHS).

[0029] In one embodiment, surrounding at least a portion of the glass surface of the glass element with the precursor P1 can be understood as exposing at least a portion of the glass surface of the glass element to the precursor P1.

[0030] In one embodiment, surrounding at least a portion of the glass surface of the glass element with the precursor P1 can be understood as subjecting at least a portion of the glass surface of the glass element to the precursor P1.

[0031] The process pressure PR1 is not particularly limited. Preferably, the process pressure PR1 is from 0.01 mbar to 500 mbar, more preferably from 0.1 mbar to 10 mbar, more preferably from 0.3 mbar to 5 mbar, more preferably from 0.6 mbar to 2.0 mbar, and even more preferably about 0.8 mbar. If the pressure is within the preferred range, the tolerance and stability of the layer composition can be further improved. Adjusting the process pressure can advantageously influence and / or guide the process temperature PT1. It is undesirable to be bound by theory; at higher pressures, more (plasma-generated) particles will collide, resulting in a temperature increase. In one embodiment of the method, the process pressure PR1 is above 0.01 mbar, above 0.1 mbar, above 0.3 mbar, above 0.6 mbar, or above 0.8 mbar. In one embodiment of the method, the process pressure PR1 is below 500 mbar, below 10 mbar, below 5 mbar, or below 2.0 mbar.

[0032] In one embodiment, the coating process is a PICVD process.

[0033] In a preferred embodiment, at least one of the following parameters is satisfied, preferably all of them:

[0034] The process temperature PT1 is 200°C to the Tg of the glass in the glass element, preferably 200°C to 500°C, more preferably 220°C to 450°C, more preferably 240°C to 320°C, and even more preferably 250°C to 300°C; and / or

[0035] ii) wherein the plasma pulse duration PD1 is 50 μs or less, preferably 40 μs or less, more preferably 30 μs or less, more preferably 20 μs or less, more preferably 15 μs or less, more preferably 12 μs or less, more preferably 8 μs or less, more preferably 6 μs or less, more preferably 4 μs or less, more preferably 3 μs or less; and / or

[0036] iii) wherein the plasma pulse duration PD1 is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, and even more preferably 6 μs or more; and / or

[0037] iv) Irradiation is performed by a microwave generator, preferably wherein the radiation has a frequency of 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably 2.45 GHz; and / or

[0038] v) Wherein the input power IP1, preferably the input power IP1 of the microwave generator, is 1000W to 10000W, more preferably 2100W to 8000W, more preferably 2500W to 6700W, more preferably 3000W to 6000W, more preferably 3200W to 5500W, and more preferably 4000W to 5000W; and / or

[0039] vi) wherein the precursor P1 comprises one or more of hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), tetramethylsilane (TMS), trimethylborazole (TMB), tris(dimethylaminosilyl)-amino-di(dimethylamino)borane (TDADB), tris(trimethylsilyl)borate (TMSB), hexamethylcyclotrisiloxane (HMCTSO), octamethylcyclotetrasiloxane (OMCTS), decamethylcyclopentasiloxane (DMCPS), dodecylcyclohexasiloxane (DMCHS), diacetoxy-di-tert-butoxysilane (DADBS), tetraethoxysilane (TEOS), tris(trimethylsiloxy)vinylsilane (TTMSVS), and vinyltriethoxysilane (VTES) and / or combinations thereof, preferably the precursor P1 is HMDSO; and / or

[0040] vii) wherein the precursor P1 comprises elements Si, C, O and H, preferably composed of elements Si, C, O and H; and / or

[0041] viii) The pulse pause PP1 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.2 ms to 2.0 ms, more preferably 0.3 ms to 1.2 ms, more preferably 0.4 to 0.8 ms; and / or

[0042] ix) The total irradiation time TT1 is 0.1 seconds or more, preferably 1 second or more, more preferably 1 second to 5 minutes, more preferably 3 seconds to 90 seconds, and even more preferably 5 seconds to 40 seconds; and / or

[0043] x) The ratio of all pulse durations PD1 [μs] to all pulse pauses PP1 [ms] [μs / ms] is 1 or more, preferably 2 or more, more preferably 2 to 50, and even more preferably 3 to 8; and / or

[0044] xi) wherein the process pressure PR1 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 10 mbar, more preferably from 0.3 mbar to 5 mbar, more preferably from 0.6 mbar to 2.0 mbar, and even more preferably from 0.8 mbar; and / or

[0045] xii) Wherein the process temperature PT1 decreases during the coating process, preferably decreasing steadily; and / or

[0046] xiii) Wherein the process temperature PT1 is at least partially, preferably at the start of the coating process, 220°C or higher, preferably 240°C or higher, more preferably 250°C or higher, more preferably 255°C or higher, more preferably 270°C or higher, more preferably 280°C or higher; and / or

[0047] xiv) wherein the flow rate of precursor P1 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 30 sccm, and even more preferably 10 to 15 sccm.

[0048] In particular, if the above parameters xii) and xiii) are satisfied, preferably i) to v), viii) and xi) to xiv), the inventors were surprised to find that the performance of the layer was further improved. If all parameters i) to xiv) are satisfied, the protection of the glass surface can be further improved. Optionally, the coating process is a plasma pulsed chemical vapor deposition (PICVD) process.

[0049] The coating process is advantageous because it provides the coated glass element with a layer that is stable to both acidic solutions and exhibits good alkali resistance. When exposed to acidic or alkaline solutions, the provided coating can exhibit long-term stability, such as three years or up to ten years. Those skilled in the art will understand that biological products can typically be stored in weakly acidic or weakly alkaline solutions (e.g., with a pH of 3 or 8). The provided coating can advantageously exhibit reduced leaching of alkali ions (e.g., [Na] ions and / or other ions derived from components in the glass), such as [Si], [B], [Al], and [Ca] ions. The provided coating can advantageously be very thin, for example, having a thickness between 20 and 100 nm, such as 40 nm.

[0050] In one embodiment, a method for coating a glass element includes the following steps:

[0051] Provide glass components including glass surfaces;

[0052] A coating process is performed on at least a portion of the glass surface, comprising the following steps:

[0053] At least a portion of the glass surface of a glass element is surrounded by a precursor P1, wherein the precursor P1 comprises the elements Si, C, O, and H; and

[0054] The precursor P1 is irradiated to generate plasma;

[0055] The following parameters must be satisfied:

[0056] The process temperature PT1 is at least partially above 220°C, wherein the process temperature PT1 decreases during the coating process; and

[0057] ii) Preferably, the pulse duration PD1 of the irradiation is less than 50 μs.

[0058] In one embodiment, the process temperature PT1 decreases during the coating process, which can be understood as occurring within the total irradiation time TT1.

[0059] It is advantageous if the process temperature PT1 is at least partially above 200°C, preferably above 220°C, and is reduced during the coating process. The coated glass element may exhibit improved alkali resistance, which may be related to the gradually changing layer on the glass surface. It is assumed that reducing the process temperature PT1 during the coating process leads to a gradual change in the layer on the glass surface, as measured by TOF-SIMS at 20% and 80% of the time required for the sputtering torch beam to reach the glass surface, [SiCH3]. + ] Count, [Si3C5H 15 O3 + ] Count and [Si2C5H 15 O2 - We can prove it by counting.

[0060] In one embodiment of the method, the process temperature PT1 is at least partially above 220°C, wherein the process temperature PT1 decreases during the coating process to a final process temperature fPT1, which is at least partially above 160°C, at least partially above 180°C, at least partially above 200°C, or at least partially above 210°C, wherein the decrease in process temperature PT1 occurs within the total irradiation time TT1.

[0061] In one embodiment of the method, the process temperature PT1 is 160°C to the Tg of the glass element, preferably 180°C to the Tg of the glass element, more preferably 200°C to the Tg of the glass element, more preferably 200°C to 500°C, more preferably 220°C to 450°C, more preferably 240°C to 320°C, and more preferably 250°C to 300°C. In one embodiment of the method, the process temperature PT1 is above 200°C, above 220°C, above 240°C, or above 250°C. In one embodiment of the method, the process temperature PT1 is below the Tg of the glass element, below 500°C, below 450°C, below 320°C, or below 300°C. It is not intended to be theoretically constrained, but it is assumed that a higher process temperature PT1 provides a coating more similar to the glass surface and / or has a thinner organic coating.

[0062] In one embodiment of the method, the coating process is plasma pulsed chemical vapor deposition (PICVD), wherein the plasma pulse duration PD1 is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, and even more preferably 6 μs or more. In one embodiment, the plasma pulse duration PD1 is less than 100 μs, less than 50 μs, less than 20 μs, or less than 10 μs. In another embodiment, the plasma pulse duration PD1 is 0.1 to 100 microseconds, 0.5 to 50 microseconds, 1 to 20 microseconds, or 6 to 10 microseconds. Microwave-assisted PICVD processes may be beneficial for coating formation and may be advantageous for providing coatings that are more resistant to leaching and / or alkali.

[0063] In one embodiment of the method, the coating process is a PICVD process, involving irradiation by a microwave generator with a radiation frequency of 300 MHz to 300 GHz, 600 MHz to 100 GHz, 800 MHz to 10 GHz, 900 MHz to 3 GHz, or approximately 2.45 GHz. In one embodiment, the radiation has a frequency of 300 MHz or higher, 600 MHz or higher, 800 MHz or higher, 900 MHz or higher, or 2.45 GHz. In another embodiment, the radiation has a frequency below 300 GHz, below 100 GHz, below 10 GHz, or below 3 GHz.

[0064] In one embodiment of the method, the coating process is a PICVD process, and the input power IP1 of the microwave generator is preferably 1000W to 10000W, more preferably 2100W to 8000W, more preferably 2500W to 6700W, more preferably 3000W to 6000W, more preferably 3200W to 5500W, and more preferably 4000W to 5000W. In one embodiment, the input power IP1 of the microwave generator is preferably 1000W or more, 2100W or more, 2500W or more, 3000W or more, 3200W or more, or 4000W or more. In another embodiment, the input power IP1 of the microwave generator is preferably 10000W or less, 8000W or less, 6700W or less, 6000W or less, 5500W or less, or 5000W or less.

[0065] In one embodiment of the method, the flow rate of precursor P1 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 30 sccm, and even more preferably 10 to 15 sccm. More preferably, precursor P1 is chemically pure, having a purity of at least 99 wt%.

[0066] In one embodiment of the method, the coating process is a PICVD process, wherein the following parameters are satisfied:

[0067] ii) The pulse duration PD1 of the plasma is 50 μs or less, preferably 40 μs or less, preferably 30 μs or less, more preferably 20 μs or less, more preferably 15 μs or less, more preferably 12 μs or less, more preferably 8 μs or less, more preferably 6 μs or less, more preferably 4 μs or less, more preferably 3 μs or less;

[0068] iii) The plasma pulse duration PD1 is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, and even more preferably 6 μs or more; and

[0069] iv) Irradiation by a microwave generator, preferably wherein the frequency of the radiation is 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably about 2.45 GHz.

[0070] In one embodiment of the method, the coating process is a PICVD process, wherein the following parameters are satisfied:

[0071] ii) The pulse duration PD1 of the plasma is 50 μs or less, preferably 40 μs or less, preferably 30 μs or less, more preferably 20 μs or less, more preferably 15 μs or less, more preferably 12 μs or less, more preferably 8 μs or less, more preferably 6 μs or less, more preferably 4 μs or less, more preferably 3 μs or less.

[0072] iii) The pulse duration PD1 of the plasma is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, and even more preferably 6 μs or more;

[0073] iv) Irradiation by a microwave generator, preferably wherein the frequency of the radiation is 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably about 2.45 GHz;

[0074] v) Wherein the input power IP1, preferably the input power IP1 of the microwave generator, is 1000W to 10000W, more preferably 2100W to 8000W, more preferably 2500W to 6700W, more preferably 3000W to 6000W, more preferably 3200W to 5500W, and more preferably 4000W to 5000W; and

[0075] viii) The pulse pause PP1 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.2 ms to 2.0 ms, more preferably 0.3 ms to 1.2 ms, and more preferably 0.4 to 0.8 ms.

[0076] Furthermore, the inventors have surprisingly discovered that pretreatment processes performed before the coating process on the glass surface to be coated can improve the adhesion of the specific layer described herein. Therefore, preferably, the method includes the following steps:

[0077] At least a portion of the glass surface of the glass element undergoes a pretreatment process, wherein the pretreatment process is one or more of the following, preferably at least plasma pretreatment, and more preferably a water washing pretreatment followed by plasma pretreatment:

[0078] Water washing pretreatment; and / or

[0079] ii) Plasma pretreatment; and / or

[0080] iii) Corona pretreatment.

[0081] Plasma treatment is particularly preferred because this pretreatment can be used on tempered glass. Furthermore, if plasma treatment is used, the same machine can be used for both the pretreatment and coating steps, reducing costs and production time. Without wishing to be bound by theory, the inventors surprisingly realized that by performing the specific pretreatment described herein, the glass surface, for example, the silanol groups on the glass surface, is activated, and then, through the specific coating process described herein, a layer with the improved properties described herein can be obtained. Therefore, in particular, the combination of pretreatment, preferably the specific plasma pretreatment described herein, and the specific coating process described herein can produce a layer with particularly improved properties, namely, excellent tolerance over a wide pH range, improved tolerance at high pH values, high chemical stability, excellent adhesion, and excellent evaporation properties.

[0082] In a preferred embodiment, the water washing pretreatment involves spraying water onto at least a portion of the glass surface, wherein one or more of the following parameters are satisfied, preferably all of them:

[0083] The spraying time is from 1 second to 5 hours, preferably from 5 seconds to 60 minutes, more preferably from 1 minute to 40 minutes, and even more preferably from 10 minutes to 40 minutes; and / or

[0084] ii) The water conductivity is from 0.1 μs / cm to 400 μs / cm, preferably from 0.5 μs / cm to 10 μs / cm, more preferably from 1 μs / cm to 5 μs / cm, and even more preferably about 2 μs / cm; and / or

[0085] iii) The water temperature is above 10°C, preferably 15°C to 100°C, more preferably 20°C to 80°C, and even more preferably 25°C to 40°C.

[0086] More preferably, all parameters i) to iii) are satisfied. In another preferred embodiment, the spraying time is more than 10 minutes, and / or the water conductivity is less than 2 μs / cm, and / or, preferably, the water temperature is at least partially above 30°C. Preferably, water is sprayed onto at least a portion of the glass surface through a needle nozzle, which preferably has an inner diameter of 0.05 mm to 5 mm, more preferably 0.5 mm to 2 mm. The water washing process is easily implemented in production. Preferably, after the water washing process, the glass surface is dried, preferably at 100 to 400°C for 1 to 100 minutes, more preferably at 200 to 300°C for 35 to 40 minutes. Preferably, the water washing pretreatment is performed before the plasma pretreatment.

[0087] In another preferred embodiment, the plasma pretreatment is a plasma-enhanced chemical vapor treatment (PECVT) process, a plasma pulsed chemical vapor treatment (PICVT) process, or a plasma-assisted chemical vapor treatment (PACVT) process, including the following steps:

[0088] The precursor P2 surrounds at least a portion of the glass surface of the glass element; and

[0089] Precursor P2 is irradiated to generate plasma;

[0090] The following parameters must be satisfied, preferably all of them:

[0091] Wherein the process temperature PT2 is from room temperature to the Tg of the glass in the glass element, preferably from room temperature to 450°C, more preferably from room temperature to 400°C, more preferably from room temperature to 320°C, and even more preferably from room temperature to 280°C; and / or

[0092] ii) wherein the plasma pulse duration PD2 is 50 ms or less, preferably 40 ms or less, more preferably 30 ms or less, more preferably 20 ms or less, more preferably 15 ms or less, more preferably 8 ms or less, more preferably 6 ms or less, more preferably 1 ms or less, more preferably 0.5 ms; and / or

[0093] iii) wherein the plasma pulse duration PD2 is 0.1 ms or more, preferably 0.2 ms or more, more preferably 0.3 ms or more, and even more preferably 0.5 ms or more; and / or

[0094] iv) Irradiation is performed by a microwave generator, preferably wherein the radiation has a frequency of 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably about 2.45 GHz; and / or

[0095] v) Wherein the input power IP2, preferably the input power IP2 of the microwave generator, is 1000W to 10000W, more preferably 2500W to 8000W, more preferably 4000W to 8000W, more preferably 5000W to 7000W, more preferably 5000W to 6500W, and more preferably 5250W to 5750W; and / or

[0096] vi) Precursor P2 includes argon, oxygen and / or nitrogen, preferably oxygen, and more preferably air; and / or

[0097] vii) wherein the precursor P2 comprises element N (e.g., N2) and / or O (e.g., O2), preferably composed thereof; preferably comprises N2 and O2, preferably composed thereof; more preferably comprises O2, preferably composed thereof; and / or

[0098] viii) The pulse pause PP2 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.5 ms to 2.0 ms, more preferably 1.5 ms to 2.0 ms, and more preferably 1.8 ms; and / or

[0099] ix) The total irradiation time TT2 is 0.1s or more, preferably 1s or more, more preferably 1s to 5min, and even more preferably 5s to 15s; and / or

[0100] x) The ratio [ms / ms] of the total pulse duration PD2 [ms] to the total pulse pause PP2 [ms] is 0.05 or more, preferably 0.1 or more, more preferably 0.15 to 5, and even more preferably 0.2 to 0.5; and / or

[0101] xi) wherein the process pressure PR2 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 100 mbar, more preferably from 0.5 mbar to 10 mbar, more preferably from 0.8 mbar to 6.0 mbar, and even more preferably from 1.0 mbar to 4.0 mbar; and / or

[0102] xii) Wherein the process temperature PT2 increases during plasma pretreatment, preferably increasing steadily; and / or

[0103] xiii) Wherein the process temperature PT2 is at least partially, preferably at the end of the plasma pretreatment process, 220°C or higher, preferably 240°C or higher, more preferably 250°C or higher, more preferably 255°C or higher, more preferably 270°C or higher, more preferably 280°C or higher; and / or

[0104] xiv) wherein the flow rate of precursor P2 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 50 sccm, and even more preferably 20 to 30 sccm.

[0105] The inventors surprisingly realized that the aforementioned performance could be further improved by using low pressure, i.e., below 10 mbar, preferably below 6.0 mbar, more preferably below 4 mbar, combined with low input power, i.e., below 8000 W, preferably below 7000 W, more preferably below 6500 W, more preferably below 5750 W. Furthermore, surface activation could be further improved if one or more parameters, preferably all parameters, were satisfied. Therefore, performance, especially the adhesion of the layer, could be improved. More preferably, the precursor P2 is chemically pure, having a purity of at least 99 wt%, preferably at least 99.995%.

[0106] In one embodiment, surrounding at least a portion of the glass surface of the glass element with the precursor P2 can be understood as exposing or subjecting at least a portion of the glass surface of the glass element to the precursor P2.

[0107] In one embodiment, the total irradiation time TT2 is the sum of the duration of the pulse and the pulse pauses.

[0108] In one embodiment, during plasma pretreatment, the process temperature PT2 increases relative to the total irradiation time TT2, preferably increasing steadily, wherein the total irradiation time TT2 is the sum of all pulse durations and pulse pauses.

[0109] In a further preferred embodiment, the corona pretreatment includes the following steps:

[0110] Position at least a portion of the glass surface of the glass element between the first and second electrodes; and

[0111] The precursor P3 surrounds at least a portion of the glass surface of the glass element; and

[0112] Apply a current C1 and / or a voltage V1 between the first and second electrodes;

[0113] The following parameters must be satisfied, preferably all of them:

[0114] The first electrode is made of brass; and / or

[0115] ii) The second electrode is made of aluminum; and / or

[0116] iii) The precursor P3 is selected from oxygen, nitrogen, air and / or mixtures thereof; and / or

[0117] iv) The process pressure PR3 is 100 mbar to 2000 mbar, preferably 500 mbar to 1500 mbar, more preferably 900 mbar to 1200 mbar; and / or

[0118] v) The energizing time is from 0.1s to 30s, preferably from 0.5s to 5s; and / or

[0119] vi) The current C1 and / or voltage V1 is from 1kV to 10kV, preferably from 2kV to 5kV; and / or

[0120] vii) The frequency of the current C1 and / or voltage V1 is 1 to 50 kHz, preferably 10 to 30 kHz, and more preferably 12 to 18 kHz.

[0121] More preferably, all parameters i) to vii) are satisfied.

[0122] In a further preferred embodiment, the pretreatment process described herein is performed before the coating process described herein. In a further preferred embodiment, the water washing pretreatment described herein is performed first, followed by the plasma pretreatment described herein, and then the coating process described herein. Preferably, the time between the pretreatment process, more preferably the plasma pretreatment process, and the coating process is less than one year, preferably less than six months, more preferably less than one day, more preferably less than one hour, more preferably less than one minute, more preferably less than 30 seconds, more preferably less than 20 seconds, more preferably less than 15 seconds; and / or more than one second, preferably more than three seconds, more preferably more than eight seconds, more preferably more than ten seconds. Therefore, the stability of the layer, especially its adhesion, can be improved.

[0123] In a further preferred embodiment, the method includes the following steps:

[0124] Post-processing is performed on at least a portion of the glass surface of the glass element, wherein the post-processing includes the following steps:

[0125] At least a portion of the glass surface of the glass element is surrounded by a precursor P4 containing argon, oxygen and / or nitrogen, preferably argon and / or oxygen; and the glass element is preferably cooled in the presence of the precursor P4, more preferably cooled to room temperature.

[0126] Preferably, post-treatment is performed after the coating process. Therefore, the performance of the layer can be further improved.

[0127] In one embodiment, surrounding at least a portion of the glass surface of the glass element with the precursor P4 can be understood as exposing or subjecting at least a portion of the glass surface of the glass element to the precursor P4.

[0128] Treated glass elements

[0129] By pretreatment as described herein, preferably PICVT pretreatment as described herein, and more preferably water washing and PICVT pretreatment as described herein, a treated glass element can be obtained. Preferably, the glass element can be obtained by the method described herein, wherein at least a portion of the glass surface of the glass element satisfies one or more of the following parameters:

[0130] The ratio of the polar portion of surface energy [mN / m] to the dispersive portion of surface energy [mN / m] is 1.4 or less, preferably 0.10 to 1.44, more preferably 0.50 to 1.40, and more preferably 1.00 to 1.35; and / or

[0131] ii) The polar portion of the surface energy is 39.50 mN / m or less, preferably 20.00 mN / m to 39.50 mN / m, more preferably 36.00 to 38.50 mN / m, and more preferably 36.50 to 38.00 mN / m; and / or

[0132] iii) The dispersive portion of the surface energy is 27.5 mN / m or more, preferably 27.50 mN / m to 40.00 mN / m, more preferably 28.00 mN / m to 35.00 mN / m, and more preferably 29.00 mN / m to 32.50 mN / m.

[0133] Surface energy is preferably determined according to DIN EN ISO 19403-1:2020-04, especially 19403-2 and 19403-5.

[0134] The inventors have surprisingly discovered that, if the aforementioned pretreatment has been performed, preferably first by performing the specific water washing pretreatment described herein, followed by the specific plasma pretreatment described herein, then the coated glass element, preferably CVD, more preferably PECVD, PICVD, or PACVD, and even more preferably PICVD coated glass element, exhibits improved layer performance, particularly stronger layer adhesion. In a further embodiment described herein, (preferably wherein the specific water washing pretreatment described herein is performed first, followed by the specific plasma pretreatment described herein) the pretreated glass element is used in a CVD coating process, more preferably in a PECVD, PICVD, or PACVD process, and even more preferably in a PICVD process. More preferably, at least a portion of the glass surface of the pretreated glass element satisfies the following parameters: i, ii, iii, i+ii, i+iii, ii+iii, or i+ii+iii.

[0135] Therefore, one embodiment of the invention relates to the use of the pretreated glass element described herein in a method including a coating process, preferably wherein the coating process includes a CVD process, more preferably PECVD, PICVD, or PACVD process, and even more preferably PICVD process. The inventors recognize that the performance of the specific layer described herein is significantly improved if pretreatment is performed. Therefore, one embodiment of the invention relates to the use of the pretreated glass element described herein in a method including the coating process described herein.

[0136] Coated glass components

[0137] An embodiment of the present invention provides a coated glass element including a glass surface.

[0138] The glass element is a container, preferably a pharmaceutical glass container;

[0139] At least a portion of the glass surface is coated;

[0140] The coating comprises at least one layer;

[0141] The coated glass containers must meet the following parameters:

[0142] After alkali treatment, the leaching amount of [Na] ions is less than 10 mg / L.

[0143] If the glass element meets these parameters, the glass surface of the glass element is adequately protected by the layer and exhibits improved stability and improved barrier properties against alkaline and acidic conditions. Therefore, the glass element is suitable for storing pharmaceutical compositions sensitive to high pH values, such as biological products. Preferably, alkali treatment is performed as described herein, and the leaching amount of [Na] ions is determined as described herein.

[0144] In a preferred embodiment, the coated glass surface meets the following parameters:

[0145] The leaching amount of [Na] ions after heat treatment and alkali treatment is less than 10 mg / L.

[0146] If this parameter is met, the protection of the container glass surface is further improved, and the container is particularly suitable for storing pharmaceutical compositions that are highly sensitive to high pH values. Preferably, heat treatment and alkali treatment are performed as described herein, and the leaching amount of [Na] ions is determined as described herein.

[0147] In a preferred embodiment, after alkali treatment, preferably after heat treatment and alkali treatment, the leaching amount of [Na] ions is less than 9 mg / L, preferably less than 7 mg / L, more preferably less than 5 mg / L, more preferably less than 4 mg / L, more preferably less than 3 mg / L, more preferably less than 2 mg / L, more preferably less than 1 mg / L, more preferably less than 0.7 mg / L, more preferably less than 0.3 mg / L, more preferably less than 0.2 mg / L, and more preferably less than 0.1 mg / L. Therefore, protection is further improved. In particular, if the leaching amount of [Na] ions is less than 0.1 mg / L, the glass element is particularly suitable for storing pharmaceutical compositions that are very sensitive to high pH values.

[0148] In a preferred embodiment, after alkali treatment, preferably after heat treatment and alkali treatment, the leaching amount of [Na] ions is 0 mg / L or more of [Na] ions, preferably 0.001 mg / L or more of [Na] ions, more preferably 0.01 mg / L or more of [Na] ions, and even more preferably 0.1 mg / L or more of [Na] ions.

[0149] A preferred embodiment of the present invention provides a coated glass element, preferably a coated glass element according to any of the foregoing embodiments, comprising a glass surface.

[0150] The glass element is a container, preferably a pharmaceutical glass container;

[0151] At least a portion of the glass surface is coated;

[0152] The coating comprises at least one layer;

[0153] The leaching amount of [Na] ions after alkali treatment is preferably a after heat treatment and alkali treatment;

[0154] Where a ≤ b*c;

[0155] If 0.9 x (full volume) of the container is ≤ 1 ml, then b is 5.00 mg / l;

[0156] If the container's 0.9 x (full volume) > 1 ml and ≤ 2 ml, then b is 4.50 mg / l;

[0157] If the container's 0.9 x (full volume) > 2 ml and ≤ 3 ml, then b is 4.10 mg / l;

[0158] If the container's 0.9 x (full volume) > 3 ml and ≤ 5 ml, then b is 3.20 mg / l;

[0159] Wherein, if the container's 0.9 x (full volume) > 5 ml and ≤ 10 ml, then b is 2.50 mg / l;

[0160] Wherein, if 0.9 x (full volume) of the container is greater than 10 ml and less than or equal to 20 ml, then b is 2.00 mg / l;

[0161] Wherein, if the container's 0.9 x (full volume) > 20 ml and ≤ 50 ml, then b is 1.50 mg / l;

[0162] Wherein, if 0.9 x (full volume) of the container is greater than 50 ml and less than or equal to 100 ml, then b is 1.20 mg / l;

[0163] Wherein, if 0.9 x (full volume) of the container is greater than 100 ml and less than or equal to 200 ml, then b is 1.00 mg / l;

[0164] Where, if 0.9 x (full volume) of the container > 200 ml and ≤ 500 ml, then b is 0.75 mg / l; and

[0165] Wherein, if 0.9 x (full volume) of the container > 500 ml, then b is 0.50 mg / l; and

[0166] Wherein c is 1.00, preferably 0.90, more preferably 0.80, more preferably 0.70, more preferably 0.60, more preferably 0.50, more preferably 0.40, more preferably 0.30, more preferably 0.20, more preferably 0.15, more preferably 0.10, more preferably 0.08, and more preferably 0.05. Since the leaching amount depends on the size of the container (see ISO 4802-2:2016(E)), the above parameters are preferred, especially for very small and very large containers. If these parameters are met, tolerance over a wide pH range, particularly tolerance at high pH values, is further improved. In a further preferred embodiment, a is 0 mg / L or more, preferably 0.001 mg / L or more, more preferably 0.01 mg / L or more, more preferably 0.1 mg / L or more, and more preferably 0.2 mg / L or more.

[0167] A preferred embodiment of the present invention provides a coated glass element, preferably a coated glass element according to any of the foregoing embodiments, comprising a glass surface.

[0168] The glass element is a container, preferably a pharmaceutical glass container;

[0169] At least a portion of the glass surface is coated;

[0170] The coating comprises at least one layer;

[0171] The coated glass containers must meet the following parameters:

[0172] The leaching amounts [mg / l] of [Si], [B], [Al] and / or [Ca] ions after 3 years of storage at pH 8 are:

[0173] [Si] ions at concentrations of 25 mg / L or less, preferably 3.7 mg / L or less, more preferably 1.0 to 3.0 mg / L; and / or, preferably and,

[0174] [B] ions at concentrations of 1.0 mg / L or less, preferably 0.5 mg / L or less, more preferably 0.001 to 0.2 mg / L; and / or, preferably, and

[0175] [Al] ions at concentrations of 1.0 mg / L or less, preferably 0.5 mg / L or less, more preferably 0.001 to 0.14 mg / L; and / or, preferably, and

[0176] [Ca] ions at concentrations of 10 mg / L or less, preferably 5 mg / L or less, and more preferably 1.0 to 4.9 mg / L.

[0177] A preferred embodiment of the present invention provides a coated glass element, preferably a coated glass element according to any of the foregoing embodiments, comprising a glass surface.

[0178] The glass element is a container, preferably a pharmaceutical glass container;

[0179] At least a portion of the glass surface is coated;

[0180] The coating comprises at least one layer;

[0181] The coated glass containers must meet the following parameters:

[0182] The leaching amount [mg / l] of [Si], [B], [Al] and / or [Ca] ions after 3 years of storage at pH 5.5 is:

[0183] [Si] ions at concentrations of 1.30 mg / L or less, preferably 1.10 mg / L or less, more preferably 0.001 to 0.60 mg / L; and / or, preferably and,

[0184] [B] ions at concentrations of 0.1 mg / L or less, preferably 0.05 mg / L or less, more preferably 0.001 to 0.004 mg / L; and / or, preferably, and

[0185] [Al] ions at concentrations below 0.1 mg / L, preferably below 0.01 mg / L, more preferably from 0.001 to 0.0004 mg / L; and / or, preferably and,

[0186] [Ca] ions at a concentration of less than 0.1 mg / L, preferably less than 0.05 mg / L, and more preferably 0.001 to 0.004 mg / L.

[0187] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after being stored at pH 5.5 for 3 years, has a leaching amount of [Si] ions of 1.30 mg / L or less, 1.10 mg / L or less, or 0.001 to 0.60 mg / L.

[0188] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after being stored at pH 5.5 for 3 years, leachates [B] ions [mg / l] at a rate of 0.1 mg / l or less, 0.05 mg / l or less, or 0.001 to 0.004 mg / l.

[0189] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after being stored at pH 5.5 for 3 years, has a leaching amount of [Al] ions [mg / l] of 0.1 mg / l or less, 0.01 mg / l or less, or 0.001 to 0.0004 mg / l of [Al] ions.

[0190] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after being stored at pH 5.5 for 3 years, leachates [Ca] ions [mg / l] at a rate of 0.1 mg / l or less, 0.05 mg / l or less, or 0.001 to 0.004 mg / l.

[0191] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after heat treatment and alkali treatment, has a leaching amount of [Na] ions of 9 mg / L or less, and after storage at pH 8 for 3 years, has a leaching amount of [Si] ions of 25 mg / L or less, 3.7 mg / L or less, or 1.0 to 3.0 mg / L.

[0192] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after heat treatment and alkali treatment, has a leaching amount of [Na] ions of 9 mg / L or less, and after storage at pH 8 for 3 years, has a leaching amount of [B] ions of 1.0 mg / L or less, 0.5 mg / L or less, or 0.001 to 0.2 mg / L.

[0193] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after heat treatment and alkali treatment, has a leaching amount of [Na] ions of 9 mg / L or less, and after storage at pH 8 for 3 years, has a leaching amount of [Al] ions of 1.0 mg / L or less, 0.5 mg / L or less, or 0.001 to 0.14 mg / L.

[0194] In one embodiment, the coated glass element is a container, preferably a pharmaceutical glass container, which, after heat treatment and alkali treatment, has a leaching amount of [Na] ions of 9 mg / L or less, and after storage at pH 8 for 3 years, has a leaching amount of [Ca] ions of 10 mg / L or less, 5 mg / L or less, or 1.0 to 4.9 mg / L.

[0195] Preferably, the leaching values ​​[mg / l] of [Si], [B], [Al] and / or [Ca] ions after storage at pH 8 and / or 5.5 for 3 years are determined as described herein.

[0196] One (preferred) embodiment of the present invention provides a coated glass element, preferably a coated glass element according to any embodiment described herein, comprising a glass surface.

[0197] At least a portion of the glass surface is coated;

[0198] The coating comprises at least one layer;

[0199] At least one layer of the coating satisfies the following parameters:

[0200] [Al + ] 80 / [Al + ] 20 ≥ 1.8;

[0201] Among them [Al + ] 20 [Al] is measured by TOF-SIMS at 20% of the time required for the sputtering gun to reach the glass surface. + ] Ion counting; and

[0202] Among them [Al + ] 80 [Al] is measured by TOF-SIMS at 80% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

[0203] If a particular glass surface is treated and coated using a specific method (such as the method described herein), then [Al] + This specific ratio of ions can be detected using the specific measurement method described herein. If this parameter is met, the layer bonds very strongly to the glass surface, and adhesion is improved. Furthermore, the glass element exhibits improved tolerance over a wide pH range, especially at high pH values, and possesses improved chemical stability.

[0204] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0205] [Al + ] 80 / [Al + ] 20 ≥ x1 [Al+] ;

[0206] Where x1 [Al+]The value is 2.0, preferably 3, more preferably 5, more preferably 7, more preferably 10, more preferably 15, more preferably 20, more preferably 25; and / or

[0207] [Al + ] 80 / [Al + ] 20 ≤ x2 [Al+] ;

[0208] Where x2 [Al+] The value is 500, preferably 200, preferably 100, more preferably 50, more preferably 40, more preferably 35, more preferably 30, more preferably 29, and more preferably 28.

[0209] If these parameters are met, adhesion, tolerance, and chemical stability will be further improved.

[0210] In one embodiment, at least one layer of the coating satisfies the following parameters:

[0211] [Al + ] 90 / [Al + ] 20 ≥ x1' [Al+] ;

[0212] Where x1' [Al+] The value is 1.8, preferably 2.0, preferably 3, more preferably 5, more preferably 7, more preferably 10, more preferably 15, more preferably 20, more preferably 25; and / or

[0213] [Al + ] 90 / [Al + ] 20 ≤ x2' [Al+] ;

[0214] Where x2' [Al+] The value is 500, preferably 200, preferably 100, more preferably 50, more preferably 40, more preferably 35, more preferably 30, more preferably 29, more preferably 28;

[0215] Among them [Al + ] 20 [Al] is measured by TOF-SIMS at 20% of the time required for the sputtering gun to reach the glass surface. + ] Ion counting; and

[0216] Among them [Al + ] 90 [Al] is measured by TOF-SIMS at 90% of the time required for the sputtering gun beam to reach the glass surface. +Ion counting.

[0217] In one embodiment, at least one layer of the coating satisfies the following parameters:

[0218] [Al + ] 90 / [Al + ] 20 ≥ x1' [Al+] ;

[0219] Where x1' [Al+] The value is 1.8, preferably 2.0, preferably 3, more preferably 5, more preferably 7, more preferably 10, more preferably 15, more preferably 20, and more preferably 25.

[0220] In one embodiment, at least one layer of the coating satisfies the following parameters:

[0221] [Al + ] 90 / [Al + ] 20 ≤ x2' [Al+] ;

[0222] Where x2' [Al+] The value is 500, preferably 200, preferably 100, more preferably 50, more preferably 40, more preferably 35, more preferably 30, more preferably 29, and more preferably 28.

[0223] In one embodiment, the present invention relates to a coated glass element comprising a glass surface.

[0224] At least a portion of the glass surface is coated.

[0225] The coating comprises at least one layer,

[0226] At least one layer of the coating satisfies the following parameters:

[0227] [Al + ] 80 / [Al + ] 20 ≥ 1.8, and / or

[0228] [Al + ] 90 / [Al + ] 20 ≥ 1.8;

[0229] Among them [Al + ] 20 [Al] is measured by TOF-SIMS at 20% of the time required for the sputtering gun to reach the glass surface. + ] Ion counting;

[0230] Among them [Al + ] 80 [Al] is measured by TOF-SIMS at 80% of the time required for the sputtering gun beam to reach the glass surface. + ] Ion counting; and

[0231] Among them [Al + ] 90 [Al] is measured by TOF-SIMS at 90% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

[0232] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0233] y1 [Al+] ≤ [Al + ] 80 / [Al + ] 60 ≤ y2 [Al+] ;

[0234] y1 [Al+] ≤ [Al + ] 60 / [Al + ] 40 ≤ y2 [Al+] ; and / or

[0235] y1 [Al+] ≤ [Al + ] 40 / [Al + ] 20 ≤ y2 [Al+] ,

[0236] Where y1 [Al+] The value is 1.01, preferably 2, more preferably 3, more preferably 5, more preferably 10, more preferably 15, more preferably 20, more preferably 25; and / or

[0237] Where y2 [Al+] The value is 500, preferably 200, preferably 100, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5; and

[0238] Among them [Al + ] 40 [Al] is measured by TOF-SIMS at 40% of the time required for the sputtering gun beam to reach the glass surface. + ] Ion counting; and

[0239] Among them [Al + ] 60 [Al] is measured by TOF-SIMS at 60% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

[0240] If these parameters are met, then [Al] + The ion count increases continuously towards the glass surface throughout the layer. This further improves adhesion, resistance, and chemical stability.

[0241] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0242] [SiCH3 + ] 20 / [SiCH3 + ] 80 ≥ x1 [SiCH3+] ;

[0243] Where x1 [SiCH3+] The value is 1.05, preferably 1.1, more preferably 1.2, more preferably 1.4, more preferably 1.6, more preferably 1.7, and more preferably 1.8; and / or

[0244] [SiCH3 + ] 20 / [SiCH3 + ] 80 ≤ x2 [SiCH3+] ;

[0245] Where x2 [SiCH3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2, and more preferably 1.8; and

[0246] Among them [SiCH3 + ] 20 The [SiCH3] value at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting; and

[0247] Among them [SiCH3 + ] 80 The [SiCH3] value is measured by TOF-SIMS at 80% of the time required for the sputtering torch beam to reach the glass surface. + Ion counting.

[0248] Therefore, adhesion, tolerance, and chemical stability are further improved. If specific precursors such as HMDSO are used in the CVD process, preferably the PICVD process, then [SiCH3] + Ions can be detected using the specific measurement methods described herein.

[0249] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0250] [SiCH3 + ] 20 / [SiCH3 + ] 90 ≥ x1' [SiCH3+] ;

[0251] Where x1' [SiCH3+] The value is 1.05, preferably 1.1, more preferably 1.2, more preferably 1.4, more preferably 1.6, more preferably 1.7, and more preferably 1.8; and / or

[0252] [SiCH3 + ] 20 / [SiCH3 + ] 90 ≤ x2' [SiCH3+] ;

[0253] Where x2' [SiCH3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2; and

[0254] Among them [SiCH3 + ] 20 The [SiCH3] value at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting; and

[0255] Among them [SiCH3 + ] 90 The [SiCH3] value is measured by TOF-SIMS at 90% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

[0256] Therefore, adhesion, tolerance, and chemical stability are further improved. If specific precursors such as HMDSO are used in the CVD process, preferably the PICVD process, then [SiCH3] + Ions can be detected using the specific measurement methods described herein.

[0257] In one (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0258] y1 [SiCH3+] ≤ [SiCH3 + ] 20 / [SiCH3 + ] 40 ≤ y2 [SiCH3+] ;

[0259] y1 [SiCH3+] ≤ [SiCH3 + ] 40 / [SiCH3 + ] 60 ≤ y2 [SiCH3+] ; and / or

[0260] y1 [SiCH3+] ≤ [SiCH3 + ] 60 / [SiCH3 + ] 80 ≤ y2 [SiCH3+] ;

[0261] Where y1 [SiCH3+] The value is 1.0, preferably 1.1, more preferably 1.2, even more preferably 1.4, and even more preferably 1.5; and / or

[0262] Where y2 [SiCH3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2, and more preferably 1.5; and

[0263] Among them [SiCH3 + ] 20 The [SiCH3] value at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting;

[0264] Among them [SiCH3 + ] 40 The [SiCH3] value at 40% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting;

[0265] Among them [SiCH3 + ] 60 The [SiCH3] value at 60% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting; and

[0266] Among them [SiCH3 + ] 80 The [SiCH3] value is measured by TOF-SIMS at 80% of the time required for the sputtering torch beam to reach the glass surface. + Ion counting.

[0267] If these parameters are met, then [SiCH3] + The ion count increases continuously towards the glass surface throughout the layer. This further improves adhesion, resistance, and chemical stability.

[0268] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0269] [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 80 ≥ x1 [Si3C5H15O3+] ;

[0270] Where x1 [Si3C5H15O3+] The value is 1.2, preferably 2, more preferably 3, more preferably 5, and even more preferably 8; and / or

[0271] [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 80 ≤ x2 [Si3C5H15O3+] ;

[0272] Where x2 [Si3C5H15O3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 15, more preferably 12, more preferably 10, more preferably 9; and

[0273] Among them, [Si3C5H] 15 O3 + ] 20 The value of [Si3C5H] at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting; and / or

[0274] Among them, [Si3C5H] 15 O3 + ] 80The value of [Si3C5H] at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + Ion counting.

[0275] If a specific precursor, such as HMDSO, is used in the CVD process, preferably the PICVD process, then [Si3C5H 15 O3 + The ions can be found in the specific TOF-SIMS measurements described in this article.

[0276] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0277] [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 90 ≥ x1' [Si3C5H15O3+] ;

[0278] Where x1' [Si3C5H15O3+] The value is 1.2, preferably 2, more preferably 3, more preferably 5, and even more preferably 8; and / or

[0279] [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 90 ≤ x2' [Si3C5H15O3+] ;

[0280] Where x2' [Si3C5H15O3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 15, more preferably 12, more preferably 10, more preferably 9; and

[0281] Among them, [Si3C5H] 15 O3 + ] 20 The value of [Si3C5H] at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting; and / or

[0282] Among them, [Si3C5H] 15 O3 + ] 90The value of [Si3C5H] at 90% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + Ion counting.

[0283] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0284] y1 [Si3C5H15O3+] ≤ [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 40 ≤ y2 [Si3C5H15O3+] ;

[0285] y1 [Si3C5H15O3+] ≤ [Si3C5H 15 O3 + ] 40 / [Si3C5H 15 O3 + ] 60 ≤ y2 [Si3C5H15O3+] ; and / or

[0286] y1 [Si3C5H15O3+] ≤ [Si3C5H 15 O3 + ] 60 / [Si3C5H 15 O3 + ] 80 ≤ y2 [Si3C5H15O3+] ;

[0287] Where y1 [Si3C5H15O3+] The value is 1.0, preferably 1.1, more preferably 1.5, more preferably 2, and even more preferably 2.0; and / or

[0288] Where y2 [Si3C5H15O3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2, and more preferably 1.5; and

[0289] Among them, [Si3C5H] 15 O3 + ] 20 The value of [Si3C5H] at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting;

[0290] Among them, [Si3C5H]15 O3 + ] 40 The value of [Si3C5H] at 40% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting;

[0291] Among them, [Si3C5H] 15 O3 + ] 60 The value of [Si3C5H] at 60% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting; and

[0292] Among them, [Si3C5H] 15 O3 + ] 80 The value of [Si3C5H] at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + Ion counting.

[0293] If these parameters are met, then [Si3C5H] 15 O3 + The ion count increases continuously towards the glass surface throughout the layer. This further improves adhesion, resistance, and chemical stability.

[0294] A preferred embodiment of the present invention provides a coated glass element comprising a glass surface.

[0295] At least a portion of the glass surface is coated;

[0296] The coating comprises at least one layer;

[0297] At least one layer of the coating satisfies the following parameters:

[0298] [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≥ 1.0;

[0299] Among them, [Si2C5H] 15 O2 - ] 20 The [Si2C5H] value was measured by TOF-SIMS at 20% of the time required for the sputtering gun beam to reach the glass surface. 15 O2- ] Ion counting; and

[0300] Among them, [Si2C5H] 15 O2 - ] 80 The [Si2C5H] value measured by TOF-SIMS at 80% of the time required for the sputtering gun beam to reach the glass surface. 15 O2 - Ion counting.

[0301] If a specific precursor, such as HMDSO, is used in the CVD process, preferably the PICVD process, then [Si2C5H 15 O2 - The ions can be detected using the specific measurement methods described herein. If this / these parameters are met, the layer bonds very strongly to the glass surface and adhesion is improved. Furthermore, the glass element exhibits improved tolerance over a wide pH range, particularly at high pH values, as well as improved chemical stability.

[0302] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0303] [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≥ x1 [Si2C5H15O2-] ;

[0304] Where x1 [Si2C5H15O2-] The value is 1.2, preferably 1.5, more preferably 2, more preferably 3, more preferably 5, more preferably 8, and more preferably 12; and / or

[0305] [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≤ x2 [Si2C5H15O2-] ;

[0306] Where x2 [Si2C5H15O2-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 25, more preferably 20, more preferably 18, more preferably 15, and more preferably 14.

[0307] If this parameter is met, adhesion, tolerance, and chemical stability will be further improved.

[0308] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0309] z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 40 ≤ z2 [Si2C5H15O2-] ;

[0310] z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 40 / [Si2C5H 15 O2 - ] 60 ≤ z2 [Si2C5H15O2-] ; and / or

[0311] z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 60 / [Si2C5H 15 O2 - ] 80 ≤ z2 [Si2C5H15O2-] ;

[0312] z1 [Si2C5H15O2-] The value is 1.0, preferably 1.1, more preferably 1.4, more preferably 1.5, more preferably 1.6, more preferably 2.0; more preferably 2.4; and / or

[0313] Where z2 [Si2C5H15O2-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 3, more preferably 2, more preferably 1.5; and

[0314] Among them, [Si2C5H] 15 O2 - ] 40 The value of [Si2C5H] at 40% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - ] Ion counting; and

[0315] Among them, [Si2C5H] 15 O2 - ] 60The value of [Si2C5H] at 60% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - Ion counting.

[0316] If these parameters are met, then [Si2C5H] 15 O2 - The ion count increases continuously towards the glass surface throughout the layer. This further improves adhesion, resistance, and chemical stability.

[0317] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0318] [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 80 ≥ x1 [Si2C3H9O3-] ;

[0319] Where x1 [Si2C3H9O3-] The value is 1.1, preferably 1.5, more preferably 2, and even more preferably 3; and / or

[0320] [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 80 ≤ x2 [Si2C3H9O3-] ;

[0321] Where x2 [Si2C3H9O3-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 8, more preferably 6, more preferably 5, more preferably 4; and

[0322] Among them, [Si2C3H9O3] - ] 20 The [Si2C3H9O3] value at 20% of the time required for the sputtering torch beam to reach the glass surface was measured using TOF-SIMS. - ] Ion counting; and

[0323] Among them, [Si2C3H9O3] - ] 80 The [Si2C3H9O3] value at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - Ion counting.

[0324] Therefore, adhesion, tolerance, and chemical stability are further improved. If specific precursors such as HMDSO are used in the CVD process, preferably the PICVD process, then [Si2C3H9O3] - Ions can be detected using the specific measurement methods described herein.

[0325] In one (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0326] x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 40 ≤ x2 [Si2C3H9O3-] ;

[0327] x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 40 / [Si2C3H9O3 - ] 60 ≤ x2 [Si2C3H9O3-] ; and / or

[0328] x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 60 / [Si2C3H9O3 - ] 80 ≤ x2 [Si2C3H9O3-] ;

[0329] Where x1 [Si2C3H9O3-] The value is 1.05, preferably 1.1, more preferably 1.5, more preferably 2, and even more preferably 3; and / or

[0330] Where x2 [Si2C3H9O3-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 3, more preferably 2, more preferably 1.5; and

[0331] Among them, [Si2C3H9O3] - ] 20 The [Si2C3H9O3] value at 20% of the time required for the sputtering torch beam to reach the glass surface was measured using TOF-SIMS. - ] Ion counting;

[0332] Among them, [Si2C3H9O3] - ] 40The [Si2C3H9O3] value at 40% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - ] Ion counting;

[0333] Among them, [Si2C3H9O3] - ] 60 The [Si2C3H9O3] value at 60% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - ] Ion counting; and

[0334] Among them, [Si2C3H9O3] - ] 80 The [Si2C3H9O3] value at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - Ion counting.

[0335] If these parameters are met, then [Si2C3H9O3] - The ion count increases continuously towards the glass surface throughout the layer. This further improves adhesion, resistance, and chemical stability.

[0336] In a (preferred) embodiment, at least one layer of the coating satisfies the following parameters:

[0337] [AlO2 - ] 90 / [AlO2 - ] 20 ≥ x1 [AlO2-] ;

[0338] Where x1 [AlO2-] The value is 1.3, preferably 1.5, more preferably 1.8, and even more preferably 2.0; and / or

[0339] [AlO2 - ] 90 / [AlO2 - ] 20 ≤ x2 [AlO2-] ;

[0340] Where x2 [AlO2-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 3, more preferably 2, more preferably 1.5; and

[0341] Among them [AlO2] - ] 20 [AlO2] was measured by TOF-SIMS at 20% of the time required for the sputtering gun beam to reach the glass surface.- ] Ion counting; and

[0342] Among them [AlO2] - ] 90 [AlO2] was measured by TOF-SIMS at 90% of the time required for the sputtering gun beam to reach the glass surface. - Ion counting.

[0343] If this parameter is met, adhesion, tolerance, and chemical stability are further improved. If a particular glass surface is treated by a specific method (such as the method described herein), then [AlO2] - This ratio of ions can be detected using the specific measurement method described herein.

[0344] The precursors and resulting compositions for the coating are not particularly limited. Preferably, the at least one layer comprises the elements Si, O, and C as measured by XPS. Therefore, the aforementioned properties can be improved. In a preferred embodiment, the at least one layer comprises SiO as measured by XPS. x C y ,

[0345] Where x is 0.3 to 3.0, preferably 0.5 to 2.0, more preferably 0.9 to 1.5; and / or

[0346] Wherein y is 0 to 6.0, preferably 0.5 to 4.0, and more preferably 2.5 to 3.5.

[0347] If this parameter is met, the above performance can be further improved.

[0348] There is no particular limitation on the thickness of this layer. Preferably, the thickness of the layer is 1 nm to 1 mm, more preferably 10 nm to 0.5 mm; more preferably 20 nm to 100 nm. If the thickness of the layer is within this range, the performance, especially the protection of the glass surface, can be improved.

[0349] There are no particular limitations on how this layer is applied to the glass surface. Preferably, the at least one layer can be obtained by a CVD process, more preferably PECVD, PICVD, or PACVD, and more preferably PICVD. Therefore, the layer bonds very strongly to the glass surface, and the adhesion is improved.

[0350] In a preferred embodiment, the at least one layer can be obtained by the method according to the embodiments described herein. The method described herein is a very cost-effective method.

[0351] In a preferred embodiment, the at least one layer is in direct contact with the glass surface of the glass element and / or the glass surface of the pretreated glass element. This improves adhesion to the glass surface. In another preferred embodiment, the at least one layer is the outermost layer and / or coating facing the inner cavity of the glass element. Therefore, protection of the glass surface is improved because the layer is in direct contact with the pharmaceutical composition.

[0352] In another preferred embodiment, the coating is a multilayer coating. Therefore, the performance of the coating can be extended. For example, a sliding layer, preferably comprising silicone resin, can be added on top of the at least one layer to improve the sliding performance of the coating.

[0353] Sealed coated glass element

[0354] One embodiment of the present invention provides a closed-type coated glass element, comprising:

[0355] Coated glass elements according to embodiments described herein; and

[0356] A closed system, preferably with a stopper and / or a cap, more preferably with a stopper and a cap.

[0357] One embodiment of the present invention provides a closed-type coated glass element, comprising:

[0358] Coated glass elements according to embodiments described herein; and

[0359] plunger and / or plunger rod; and / or

[0360] A closed system, preferably a tip cap and / or needle shield.

[0361] In a preferred embodiment, the sealed coated glass element passed the container closure integrity test according to DIN EN ISO 8871-5:2016; Chapter 4.4 in conjunction with Annex D. Therefore, the safe transport of the pharmaceutical composition can be ensured.

[0362] According to one embodiment of the present invention, a filled coated glass element comprises:

[0363] Coated glass elements according to embodiments described herein; and

[0364] The composition, preferably a pharmaceutical composition, more preferably a composition containing a biological product (e.g., a peptide or protein, including antibodies) or mRNA. Preferably, the composition is a liquid composition having a pH value of 7 or higher, preferably 8 to 14, more preferably 8 to 10. In a preferred embodiment, the composition contains one or more compounds expressly mentioned in WO2018 / 157097A1, which is incorporated herein by reference.

[0365] There is no particular limitation on the time required for the sputtering gun to reach the glass surface. This time depends particularly on the layer thickness and layer stability. Preferably, the time required for the sputtering gun to reach the glass surface is 0.5 to 60 minutes, more preferably 1 to 10 minutes, and even more preferably 2 to 4 minutes; and / or, in the case of measuring positive ions, the point at which the sputtering gun reaches the glass surface is [Al]. + ] Ion counting and [Si + The point at which the ratio of ion counts equals or first exceeds the value of 0.10; and / or, in the case of measuring negative ions, the point at which the sputtering gun reaches the glass surface is [AlO2]. - ] Ion counting and [Si - The ratio of ion counts equals or first exceeds the value of 0.10; and / or the ion count, preferably of [AlO2] ions. - [Si2C3H9O3] - [Si2C5H] 15 O2 - [Si3C5H] 15 O3 + ]、[Al + ] and / or [SiCH3 + The count can be obtained using the specific method described herein. If the time is within the above range, performance can be improved, particularly for the protection of the glass surface.

[0366] There are no particular restrictions on the glass used in the glass element. Preferably, the glass is borosilicate glass, aluminosilicate glass, lithium-aluminosilicate (LAS) glass, and more preferably borosilicate glass. Therefore, the strong adhesion of the at least one layer can be improved.

[0367] In a preferred embodiment, the glass composition comprises, in mass %:

[0368] SiO2: 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%; and / or

[0369] B2O3: 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%; and / or

[0370] Al2O3: 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%; and / or

[0371] X₂O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, and Li, preferably X is Na and / or K; and / or

[0372] YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg.

[0373] More preferably, the glass composition, in mass percent, consists of the following:

[0374] SiO2: 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%;

[0375] B2O3: 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%;

[0376] Al2O3: 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%;

[0377] X2O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, and Li, and preferably X is Na and / or K;

[0378] YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg; and

[0379] Preferably remove unavoidable impurities.

[0380] In another preferred embodiment, the glass composition comprises, in mass percent:

[0381] SiO2: 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%; and / or

[0382] B2O3: 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%; and / or

[0383] Al2O3: 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%; and / or

[0384] X₂O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, and Li, preferably X is Na and / or K; and / or

[0385] YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg.

[0386] More preferably, the glass composition, in mass percent, consists of the following:

[0387] SiO2: 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%;

[0388] B2O3: 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%;

[0389] Al2O3: 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%;

[0390] X2O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, and Li, and preferably X is Na and / or K;

[0391] YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg; and

[0392] Preferably remove unavoidable impurities.

[0393] There are no particular limitations on the shape of the glass element. The shape can be a tube, rod, plate, and / or container. Preferably, the glass element is a container, more preferably a pharmaceutical container, even more preferably a vial, syringe, ampoule, or cartridge, and even more preferably a vial. Even when developed for pharmaceutical packaging, coated glass elements can be used in the automotive, aircraft, technical tubing, and many other technical fields due to their improved performance.

[0394] If the glass element is a container, the volume of the container is not particularly limited. Preferably, the full volume of the container is 0.1 ml to 1000 ml, more preferably 0.5 ml to 500 ml, more preferably 1 ml to 250 ml, more preferably 2 ml to 30 ml, more preferably 2 ml to 15 ml, more preferably about 1 ml, 2 ml, 3 ml, 4 ml, 5 ml, 6 ml, 7 ml, 8 ml, 9 ml, 10 ml, 11 ml, 12 ml, 13 ml, 14 ml or 15 ml; more preferably 5 to 15 ml.

[0395] The location of at least a portion of the glass surface is not particularly limited. Preferably, the glass element includes an inner surface, more preferably a tube or container, and more preferably a container, wherein the inner surface includes at least a portion of the glass surface, preferably at least a portion of the glass surface. Thus, if a pharmaceutical composition is present in the container, the inner surface of the glass element is effectively protected.

[0396] In another preferred embodiment, the glass element includes an outer surface, preferably wherein the glass element is a tube or container, more preferably a container, and wherein the outer surface includes at least a portion of the glass surface, preferably at least a portion of the glass surface.

[0397] In a preferred embodiment, the glass element is a vial or cartridge comprising a cylindrical portion, a neck, and a crown, wherein at least the inner surface of the cylindrical portion is coated. Therefore, if a pharmaceutical composition is present in the container, the inner surface of the glass element is effectively protected.

[0398] In a preferred embodiment, at least a portion of the glass surface of the container includes at least a portion of the inner surface of the container. Preferably, at least a portion of the glass surface of the container is the surface in contact with the liquid when the container stands stably on the ground and is filled with liquid, wherein the liquid volume relative to the full volume of the container [vol. / vol.] is 10% or more, preferably 30% or more, more preferably 90% or more.

[0399] In a preferred embodiment, the glass element is a vial or syringe comprising a cylindrical portion, a neck, and a crown, wherein the crown, preferably and the neck, are uncoated; and / or the glass element is a syringe comprising a flange, a cylindrical portion, and a tip, preferably and a needle, wherein the needle, preferably and the flange, more preferably and the tip, are uncoated. Therefore, the presence of such a glass element improves the storage stability of the pharmaceutical composition.

[0400] definition

[0401] Unless otherwise stated, the following definitions apply throughout the specification and claims:

[0402] The layers described herein are layers that can be obtained through a coating process, preferably including the coating process described herein. In a coating process, the precursor and process parameters (e.g., pulse duration in the PICVD process) remain unchanged. Therefore, for example, a single layer as described herein can be produced using a PICVD process with one precursor and one continuous coating step.

[0403] In this document, a coating process is a process in which at least one layer is applied to a glass surface. Preferably, the layer is applied by a CVD coating process, more preferably by PECVD, PICVD, or PACVD processes, and even more preferably by PICVD. Preferably, one layer can be obtained by one coating process. Pretreatment is not a coating process here. Preferably, all parameters mentioned herein refer to the same layer within the coating.

[0404] Unavoidable impurities in this article are impurities that may be contained in the segregated material, such as Fe, Ti, Zn, Cu, Mn, and Co. Preferably, the total amount of all unavoidable impurities is 5% by weight or less, more preferably 2.5% by weight or less, more preferably 1.0% by weight or less, more preferably 0.5% by weight or less, more preferably 0.1% by weight or less, and more preferably 0.01% by weight or less.

[0405] The total irradiation time here is the sum of the duration of the pulses and the pulse pauses. The ambient temperature and pressure here are 20°C and 1.0 bar.

[0406] Unless otherwise stated, [R] in this article refers to... ttThis is the count of [R] ions at tt% of the time required for the sputtering gun to reach the glass surface, measured by TOF-SIMS. Preferably, all [R] ions... tt The value is determined as described in this article.

[0407] The temperature referred to in this process is the temperature measured in the middle of the glass element using a pyrometer. If the glass element is a container, the temperature is measured in the middle of the cylindrical part of the container (e.g., a vial).

[0408] Unless otherwise specified, the input power is the positive power measured between the irradiation generator, such as a microwave generator, and the glass element, for example, by a MW diode (ACTP-1502; 10 dB damping).

[0409] Parameters and methods

[0410] Transition temperature Tg

[0411] The transition temperature Tg here can preferably be measured by differential scanning calorimetry (DSC).

[0412] Surface energy

[0413] Surface energy was determined according to DIN EN ISO 19403-1:2020-04, particularly 19403-2 and 19403-5. Water, diiodomethane, and / or n-hexadecane were used as reference solutions.

[0414] Heat treatment

[0415] The heat treatment described herein refers to tempering the glass elements at 330°C for 60 minutes in a preheated oven under ambient pressure. For alkali treatment, either heat-treated or untreated glass elements may be used. Unless otherwise specified, the glass elements are untreated.

[0416] Alkali treatment

[0417] The alkali treatment is as follows:

[0418] Provide a heat-treated or untreated glass container. If the container has two openings, such as a syringe, the smaller opening is covered with a closure, such as a tip cap. Then fill the container with 0.9 x (full volume) of a 0.005 mol / L KOH solution (KOH: potassium hydroxide hydrate ≥99.995%, Suprapur® (Merck), softened water (similar to ultrapure water of purity ≤0.1 µS / cm at 25°C according to DIN ISO 3696), seal it with a stopper, and then insert the container into an autoclave (e.g., Systec, model DX-150 (PM-CA-0001-01)) and treat it at 121°C and 1 bar above ambient pressure (e.g., 2 bar) for 3 hours. After this, empty the container and wash it twice with deionized water.

[0419] Leaching amount of [Na] ions:

[0420] The leaching amount of [Na] ions [mg / l] here can be obtained as follows:

[0421] As described above, after the alkali treatment, preferably after the heat treatment and alkali treatment, a 0.9 x (full volume) mL solution of 0.1 mol / L HCl (30% Suprapur® (Merck) hydrochloric acid) diluted with softened water (similar to ultrapure water with a purity of ≤0.1 µS / cm at 25°C according to DIN ISO 3696) is filled into the container, and the container is sealed with a stopper. The container is then reinserted into an autoclave (e.g., Systec, model DX-150 (PM-CA-0001-01)) and treated at 121°C and 1 bar above ambient pressure for 6 hours. Subsequently, the [Na] ion concentration in the 0.1 mol / L HCl solution is determined by FAAS analysis using, for example, a Varian SpectrAA 280 FS (PE 3-004) to obtain the [Na] ion leaching value [mg / L].

[0422] Leaching amounts of [Si], [B], [Al], and [Ca] ions after 3 years of storage at pH 8 [mg / l]

[0423] The leaching values ​​[mg / l] of [Si], [B], [Al], and [Ca] ions after 3 years of storage at pH 8 can be obtained as follows:

[0424] A heat-treated or unheat-treated glass container is provided. If the container has two openings, such as a syringe, the smaller opening is covered with a closure, such as a tip cap. Then, 0.2 x (full volume) of a sodium bicarbonate solution with a pH of 8 (336.04 g of NaHCO3 diluted in 4 liters of softened water (similar to ultrapure water of purity 1 with a purity ≤0.1 µS / cm at 25°C according to DIN ISO 3696) is added to the container, and the container is sealed with a stopper. The container is then stored in an oven at 25°C for 3 years. Afterward, the concentrations of [B], [Ca], [Si], and [Al] ions in the bicarbonate solution are determined by ICP-MS (Agilent 7500ce) to obtain the leaching values ​​[mg / L] of [B], [Ca], [Si], and [Al] ions in the bicarbonate solution.

[0425] Leaching amounts of [Si], [B], [Al], and [Ca] ions after 3 years of storage at pH 5.5 [mg / l]

[0426] A heat-treated or unheat-treated glass container is provided. If the container has two openings, such as a syringe, the smaller opening is covered with a closure, such as a tip cap. Then, 0.2 x (fill volume) of ultrapure water with a pH of 5.5 and a purity of 1 (≤0.1 µS / cm at 25°C, similar to DIN ISO 3696) is added to the container, and the container is sealed with a stopper. The container is then stored in an oven at 25°C for 3 years. The concentrations of [B], [Ca], [Si], and [Al] ions in the aqueous solution are then determined by ICP-MS (Agilent 7500ce) to obtain the concentrations of [B], [Ca], [Si], and [Al] ions in the aqueous solution. + The leaching amount of ions [mg / l].

[0427] TOF-SIMS

[0428] The following details the measurement methods and data evaluation for specific TOF-SIMS measurements. Ions, such as [Al] ions... + ] 20 、[Al + ] 80 [Si2C5H] 15 O2 - ] 20 and [Si2C5H 15 O2 - ] 80 The value can be obtained from the following description.

[0429] Measurement methods

[0430] For measurement, TOF SIMS (TOF.SIMS 5 from Iontof) can be used. Unless otherwise stated, TOF-SIMS is measured according to ASTM E 1829 and ASTM E 2695.

[0431] The following parameter settings are used for TOF-SIMS:

[0432] For analysis:

[0433] Primary ion: Bi 3+ ;

[0434] Energy: 30000 eV;

[0435] Measurement area: 200 x 200 µm 2 ;

[0436] Pattern: 128 x 128 Random; and

[0437] Bismuth analysis current: 0.3 pA.

[0438] For the splash gun (Argon Cluster source):

[0439] Sputtered ions: Ar1051 (argon);

[0440] Energy: 5000eV;

[0441] Sputtering area: 500 x 500 µm 2 ;and

[0442] The sputtering flow of the Ar-cluster source: 1 nA.

[0443] also:

[0444] Cycle time: 200 µs

[0445] Analyzer extractor: 2160V;

[0446] Analyzer detector: 9000V;

[0447] Charge compensation: immersion electron gun (flood gun);

[0448] First ion time-of-flight correction: On; and

[0449] Air drive: 9 x 10 -7 mbar.

[0450] A sample of a coated glass element, such as one half of an internal coated container cut longitudinally into two pieces, is positioned such that the centerlines of the TOF-SIMS sputtering gun and the liquid metal ion gun strike the coated area of ​​the sample, such that the sputtering area covers the entire measurement area. Preferably, the centerlines of the TOF-SIMS sputtering gun and the liquid metal ion gun strike the same point in the coated area of ​​the sample. TOF-SIMS measures either positive or negative ions. To obtain both types of ions, two measurements can be performed, each using a new area of ​​the same sample or a new sample, such as the front and rear halves of a longitudinally cut coated container.

[0451] Data evaluation

[0452] For data evaluation, the counts of all ions are normalized to [Si]. + ] ions and [Si - ] ions, of which [Si + ] ions and [Si - The ions are each set to 1 (see, for example, Table 1 and...). Figure 4 ).

[0453] Furthermore, the starting point (sputtering time) of the TOF SIMS analysis was set to 0%, and the point at which the sputtering time reached the glass surface was set to 100%. This was determined by [Al]. + ] signal and [AlO2 - The signals are represented because these signals can be clearly assigned to the glass.

[0454] In the case of measuring positive ions, the point at which the sputtering gun reaches the glass surface can be, preferably, [Al]. + ] Ion counting and [Si + The point at which the ratio of ion counts equals or first exceeds the value of 0.10.

[0455] In the case of measuring negative ions, the point at which the sputtering gun reaches the glass surface can be, preferably, [AlO2]. - ] Ion counting and [Si - The point at which the ratio of ion counts equals or first exceeds the value of 0.10.

[0456] For example, such as Figure 4 As shown in Table 1, the starting point for the analysis (i.e., the measurement process) is set to 0% of the time required for the sputtering analysis process to reach the glass surface. At this point, [Al] + ] Ion counting and [Si + The ratio of the number of ions counts can be, preferably, 0.00. After a certain analysis time (sputtering time), [Al] + ] Ion counting and [Si +The ratio of ion counts is greater than 0.10. Since aluminum is explicitly designated as a glass element, this point represents the time required for the sputtering torch beam to reach the glass surface. Up to this point, the ratio has never reached greater than 0.10 (see...). Figure 4 Therefore, this point was set to 100%, because this is 100% of the time required for the sputtering analysis process to reach the glass surface. Attached Figure Description

[0457] There are several methods for advantageously designing and further developing the teachings of the invention. For this purpose, reference is made, on the one hand, to the patent claims dependent on the independent patent claims, and to the following explanation of preferred examples of embodiments of the invention shown in the accompanying drawings; on the other hand, reference is made to the supplementary solutions. Further developments of the general preferred embodiments and teachings will be explained in conjunction with the explanation of preferred embodiments of the invention with the aid of the accompanying drawings:

[0458] Figure 1 : A schematic side view of an embodiment of the present invention;

[0459] Figure 2 : A schematic side view of an embodiment of the present invention;

[0460] Figure 3 A block diagram of a method according to an embodiment of the present invention;

[0461] Figure 4 The results of Example 1 (positive ion) measured by TOF-SIMS described in this article;

[0462] Figure 5 The results of Example 1 (negative ions) measured by TOF-SIMS described in this article;

[0463] Figure 6 The results of Example 3 (positive ion) measured by TOF-SIMS described in this article;

[0464] Figure 7 The results of Example 3 (negative ions) measured by TOF-SIMS described in this article. Detailed Implementation

[0465] Example 1 (Example of an Invention)

[0466] Unless otherwise specified, Example 1 is prepared according to EP 0 821 079 A1, EP 0 811 367 A2, WO 03 015122 A1 and EP 2 106 461 A1:

[0467] Two 10 R vials (pure EVERIC from SCHOTT AG) were provided. TMAs a first pretreatment, a water pretreatment was performed, in which the vials were washed in a laboratory dishwasher (HAMO AG LS-2000) at room temperature with ultrapure water at 25°C for 2 minutes, washed at 40°C for 6 minutes, and then washed at room temperature for 25 minutes. Afterwards, the vials were dried at 300°C for 20 minutes.

[0468] Subsequently, two vials were simultaneously processed and coated using equipment according to WO 03015122 A1. For all plasma treatments, microwave irradiation at a frequency of 2.45 GHz was used. The reaction chamber was the interior of the vial. The ambient conditions outside the vial were dominant.

[0469] First, the inside of the vials was evacuated until a pressure of 0.05 mbar was reached. Then, oxygen was filled into the vials (for two vials, flow rate: 50 sccm) until a pressure of 5 mbar was reached, and plasma pretreatment began. The plasma was excited in pulsed mode with an input power of 6700 W (for two vials), a pulse duration of 0.5 ms, and a pulse pause of 1.8 ms. Plasma pretreatment lasted for 14 seconds until the temperature of the vials reached 280 °C, measured using a pyrometer at the midpoint of the cylindrical section of the vial.

[0470] The coating process followed immediately. Vials were filled with HMDSO (flow rate: 25 sccm for two vials) at a pressure of 0.8 mbar. The vials were then irradiated for 0.2 seconds (pressure: 0.8 mbar, flow rate: 25 sccm HMDSO for two vials, input power: 6000 W, pulse duration: 0.050 ms, pulse pause: 30 ms), followed by irradiation for 50 seconds (pressure: 0.8 mbar, flow rate: 25 sccm HMDSO for two vials, input power: 3250 W, pulse duration: 0.003 ms, pulse pause: 1 ms).

[0471] Next, post-processing is performed, which involves filling the vials with argon gas and cooling them to room temperature in the presence of argon gas to obtain two vials with the same coating.

[0472] Example 2 (Example of an Invention)

[0473] Unless otherwise specified, Embodiment 2 is prepared according to EP 0 821 079 A1, EP 0 811 367 A2, WO 03 015122 A1 and EP 2 106 461 A1:

[0474] Two 10 R vials (pure EVERIC from SCHOTT AG) are provided. TMAs a first pretreatment, a water pretreatment was performed, in which the vials were washed in a laboratory dishwasher (HAMO AG LS-2000) at room temperature with ultrapure water at 25°C for 2 minutes, washed at 40°C for 6 minutes, and then washed at room temperature for 25 minutes. Afterwards, the vials were dried at 300°C for 20 minutes.

[0475] Subsequently, two vials were simultaneously processed and coated using equipment according to WO 03015122 A1. For all plasma treatments, microwave irradiation at a frequency of 2.45 GHz was used. The reaction chamber was the interior of the vial. The ambient conditions outside the vial were dominant.

[0476] First, the inside of the vials was evacuated until a pressure of 0.05 mbar was reached. Then, oxygen was filled into the vials (for two vials, flow rate: 50 sccm) until a pressure of 1.2 mbar was reached, and plasma pretreatment began. The plasma was excited in pulsed mode with an input power of 5500 W, a pulse duration of 0.5 ms, and a pulse pause of 1.8 ms. Plasma pretreatment lasted for 27 seconds until the temperature of the vials reached 280°C, measured using a pyrometer at the midpoint of the cylindrical section of the vial.

[0477] The coating process began immediately after 11 seconds. Vials were filled with HMDSO (flow rate for two vials: 25 sccm) and the pressure was set to 0.8 mbar. The vials were then irradiated for 0.2 seconds (pressure: 0.8 mbar, flow rate for two vials: 25 sccm HMDSO, input power: 6000 W, pulse duration: 0.050 ms, pulse pause: 30 ms) followed by 11 seconds (pressure: 0.8 mbar, flow rate for two vials: 25 sccm HMDSO, input power: 4500 W, pulse duration: 0.008 ms, pulse pause: 0.5 ms). After the coating process, the temperature of the vials was 280°C, measured using a pyrometer at the midpoint of the cylindrical portion of the vial.

[0478] Next, post-processing is performed, which involves filling the vials with oxygen and cooling them to room temperature in the presence of oxygen to obtain two identical coated vials.

[0479] Example 3 (Comparison Example)

[0480] Example 3 is a SCHOTT Type I plus® 10R glass vial.

[0481] TOF-SIMS Measurement

[0482] The results of Example 1 of the TOF-SIMS measurements described in this article are summarized in Tables 1 and 2 and depicted in... Figure 4 and 5 The results of Example 3 of the TOF-SIMS measurements described in this paper are summarized in Tables 3 and 4 and depicted in... Figure 6 and Figure 7 middle.

[0483] Table 1 Example 1: Positive Ions

[0484]

[0485] Table 2 Example 1: Negative Ions

[0486]

[0487] Table 3 Example 3: Positive Ions

[0488]

[0489] Table 4 Example 3: Negative Ions

[0490]

[0491] Leaching amount of [Na] ions

[0492] The results of Examples 1 to 3 of the [Na] ion leaching amounts described in this article are summarized in Table 5:

[0493] Table 5: Leaching amount of [Na] ions

[0494]

[0495] Leaching amounts of [Si], [B], [Al] and [Ca] ions after 3 years of storage at pH 8 and pH 5.5

[0496] The results of the leaching amounts [mg / l] of [Si], [B], [Al] and [Ca] ions described in this paper after 3 years of storage at pH 8 are summarized in Table 6:

[0497] Table 6: Leaching amounts of [Si], [B], [Al], and [Ca] ions after 3 years of storage at pH 8 [mg / l]

[0498]

[0499] The results of the leaching amounts [mg / l] of [Si], [B], [Al] and [Ca] ions described in this paper after 3 years of storage at pH 5.5 are summarized in Table 7:

[0500] Table 7: Leaching amounts of [Si], [B], [Al], and [Ca] ions after 3 years of storage at pH 5.5 [mg / l]

[0501]

[0502] In the following description of the embodiments, the same reference numerals denote similar parts.

[0503] Figure 1 and 2 A schematic side view of an embodiment of the present invention is depicted. Figure 1 In the depicted image, glass surface 1 is partially coated with coating 2. The coating shown is a single layer. Therefore, the coating is in direct contact with glass surface 1 and is the outermost layer. Figure 2 In this process, the partially pretreated glass surface 3 is partially coated with coating 2. The coating depicted is a single layer. Therefore, the coating is in direct contact with the glass surface 1 and is the outermost layer.

[0504] Figure 3 A block diagram of a method according to an embodiment of the present invention is shown. After pretreatment 1001, a coating process 1002 is performed. Posttreatment 1003 may then be performed.

[0505] Figures 4 to 7 The results of TOF-SIMS measurements are shown. Some of the values ​​depicted in these figures can be found in Tables 1 through 4. It can be seen that the example of this invention ( Figure 4 and 5 The values ​​in Example 1) change significantly during sputtering, while in the comparative example (Example 3), these values ​​are constant for most of the sputtering time, and then change rapidly after 90% of the time required for the sputtering gun beam to reach the glass surface.

[0506] plan

[0507] In summary, the embodiments and preferred embodiments are as follows. The scope of protection is defined by the claims. Combinations of two or more embodiments, such as combinations of 3, 4, or 8 embodiments, are further preferred. The definitions and general statements herein preferably also apply to the following embodiments and preferred embodiments.

[0508] A method for coating glass components includes the following steps:

[0509] Provide glass components including glass surfaces; and

[0510] A coating process is performed on at least a portion of the glass surface, comprising the following steps:

[0511] The precursor P1 surrounds at least a portion of the glass surface of the glass element; and

[0512] Precursor P1 is irradiated to generate plasma;

[0513] The following parameters must be satisfied, preferably both:

[0514] The process temperature PT1 is above 200℃; and / or

[0515] ii) The irradiation pulse duration PD1 is less than 50 µs.

[0516] According to the method described in the aforementioned scheme, the coating process is a plasma-enhanced chemical vapor deposition (PECVD) process, a plasma pulsed chemical vapor deposition (PICVD) process, or a plasma-assisted chemical vapor deposition (PACVD) process, preferably a plasma pulsed chemical vapor deposition (PICVD) process.

[0517] According to any one of the foregoing schemes, the process temperature PT1 is 200°C to the Tg of the glass element, preferably 200°C to 500°C, more preferably 220°C to 450°C, more preferably 240°C to 320°C, and even more preferably 250°C to 300°C.

[0518] According to any one of the foregoing schemes, the plasma pulse duration PD1 is 50 μs or less, preferably 40 μs or less, more preferably 30 μs or less, more preferably 20 μs or less, more preferably 15 μs or less, more preferably 12 μs or less, more preferably 8 μs or less, more preferably 6 μs or less, more preferably 4 μs or less, more preferably 3 μs or less; and / or

[0519] The plasma pulse duration PD1 is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, and even more preferably 6 μs or more.

[0520] According to any one of the foregoing schemes, the irradiation is performed by a microwave generator, preferably wherein the radiation has a frequency of 300MHz to 300GHz, more preferably 600MHz to 100GHz, more preferably 800MHz to 10GHz, more preferably 900MHz to 3GHz, and more preferably 2.45GHz.

[0521] According to any one of the preceding items, the input power IP1 of the irradiation generator is preferably 1000W to 10000W, more preferably 2100W to 8000W, more preferably 2500W to 6700W, more preferably 3000W to 6000W, more preferably 3200W to 5500W, and more preferably 4000W to 5000W.

[0522] According to any one of the foregoing schemes, the precursor P1 comprises one or more and / or combinations of hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), tetramethylsilane (TMS), trimethylborazole (TMB), tris(dimethylaminosilyl)-amino-di(dimethylamino)borane (TDADB), tris(trimethylsilyl)borate (TMSB), hexamethylcyclotrisiloxane (HMCTSO), octamethylcyclotetrasiloxane (OMCTS), decamethylcyclopentasiloxane (DMCPS), dodecylcyclohexasiloxane (DMCHS), diacetoxyditert-butoxysilane (DADBS), tetraethoxysilane (TEOS), tris(trimethylsiloxy)vinylsilane (TTMSVS), and vinyltriethoxysilane (VTES), preferably HMDSO; and / or

[0523] The precursor P1 contains elements Si, C, O and H, preferably composed of elements Si, C, O and H.

[0524] According to any one of the foregoing schemes, the process pressure PR1 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 10 mbar, more preferably from 0.3 mbar to 5 mbar, more preferably from 0.6 mbar to 2.0 mbar, and even more preferably from 0.8 mbar.

[0525] According to any one of the foregoing schemes, the method is preferably wherein the coating process is a plasma pulsed chemical vapor deposition (PICVD) process, wherein at least one of the following parameters is satisfied, preferably all of them are satisfied:

[0526] The process temperature PT1 is 200°C to the Tg of the glass in the glass element, preferably 200°C to 500°C, more preferably 220°C to 450°C, more preferably 240°C to 320°C, and even more preferably 250°C to 300°C; and / or

[0527] ii) wherein the plasma pulse duration PD1 is 50 μs or less, preferably 40 μs or less, more preferably 30 μs or less, more preferably 20 μs or less, more preferably 15 μs or less, more preferably 12 μs or less, more preferably 8 μs or less, more preferably 6 μs or less, more preferably 4 μs or less, more preferably 3 μs or less; and / or

[0528] iii) wherein the plasma pulse duration PD1 is 0.1 μs or more, preferably 0.5 μs or more, more preferably 1 μs or more, and even more preferably 6 μs or more; and / or

[0529] iv) Irradiation is performed by a microwave generator, preferably wherein the radiation has a frequency of 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably 2.45 GHz; and / or

[0530] v) Wherein the input power IP1, preferably the input power IP1 of the microwave generator, is 1000W to 10000W, more preferably 2100W to 8000W, more preferably 2500W to 6700W, more preferably 3000W to 6000W, more preferably 3200W to 5500W, and more preferably 4000W to 5000W; and / or

[0531] vi) wherein the precursor P1 comprises one or more of hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), tetramethylsilane (TMS), trimethylborazole (TMB), tris(dimethylaminosilyl)-amino-di(dimethylamino)borane (TDADB), tris(trimethylsilyl)boronic acid ester (TMSB), hexamethylcyclotrisiloxane (HMCTSO), octamethylcyclotetrasiloxane (OMCTS), decamethylcyclopentasiloxane (DMCPS), dodecylcyclohexasiloxane (DMCHS), diacetoxyditert-butoxysilane (DADBS), tetraethoxysilane (TEOS), tris(trimethylsiloxy)vinylsilane (TTMSVS), and vinyltriethoxysilane (VTES) and / or combinations thereof, preferably the precursor P1 is HMDSO; and / or

[0532] vii) wherein the precursor P1 comprises elements Si, C, O, and H, preferably composed of elements Si, C, O, and H; and / or

[0533] viii) The pulse pause PP1 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.2 ms to 2.0 ms, more preferably 0.3 ms to 1.2 ms, more preferably 0.4 ms to 0.8 ms; and / or

[0534] ix) The total irradiation time TT1 is 0.1s or more, preferably 1s or more, more preferably 1s to 5min, more preferably 3s to 90s, and more preferably 5s to 40s; and / or

[0535] x) The ratio of all pulse durations PD1 [μs] to all pulse pauses PP1 [ms] [μs / ms] is 1 or more, preferably 2 or more, more preferably 2 to 50, and even more preferably 3 to 8; and / or

[0536] xi) wherein the process pressure PR1 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 10 mbar, more preferably from 0.3 mbar to 5 mbar, more preferably from 0.6 mbar to 2.0 mbar, and more preferably from 0.8 mbar; and / or

[0537] xii) wherein the process temperature decreases during the coating process, preferably decreasing steadily; and / or

[0538] xiii) wherein the process temperature PT1 is at least partially, preferably at the start of the coating process, 220°C or higher, preferably 240°C or higher, more preferably 250°C or higher, more preferably 255°C or higher, more preferably 270°C or higher, and more preferably 280°C or higher; and / or

[0539] xiv) wherein the flow rate of precursor P1 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 30 sccm, and even more preferably 10 to 15 sccm.

[0540] A method, preferably a method according to any of the foregoing schemes, includes the following steps:

[0541] At least a portion of the glass surface of the glass element undergoes a pretreatment process, wherein the pretreatment process is one or more of the following, preferably first performing a water washing pretreatment, followed by a plasma pretreatment:

[0542] Water washing pretreatment; and / or

[0543] ii) Plasma pretreatment; and / or

[0544] iii) Corona pretreatment.

[0545] According to the method described in any one of the foregoing schemes,

[0546] The water washing pretreatment involves spraying water onto at least a portion of the glass surface, wherein one or more of the following parameters are satisfied, preferably all of them:

[0547] The spraying time is from 1 second to 5 hours, preferably from 5 seconds to 60 minutes, more preferably from 1 minute to 40 minutes, and even more preferably from 10 minutes to 40 minutes; and / or

[0548] ii) The water conductivity is from 0.1 μs / cm to 400 μs / cm, preferably from 0.5 μs / cm to 10 μs / cm, more preferably from 1 μs / cm to 5 μs / cm, and even more preferably about 2 μs / cm; and / or

[0549] iii) The water temperature is above 10°C, preferably 15°C to 100°C, more preferably 20°C to 80°C, and even more preferably 25°C to 40°C.

[0550] According to the method described in any one of the foregoing schemes,

[0551] The plasma pretreatment includes plasma-enhanced chemical vapor treatment (PECVT), plasma pulsed chemical vapor treatment (PICVT), or plasma-assisted chemical vapor treatment (PACVT), and comprises the following steps:

[0552] The precursor P2 surrounds at least a portion of the glass surface of the glass element; and

[0553] Precursor P2 is irradiated to generate plasma;

[0554] The following parameters must be satisfied, preferably all of them:

[0555] Wherein the process temperature PT2 is from room temperature to the Tg of the glass in the glass element, preferably from room temperature to 450°C, more preferably from room temperature to 400°C, more preferably from room temperature to 320°C, and even more preferably from room temperature to 280°C; and / or

[0556] ii) wherein the plasma pulse duration PD2 is 50 ms or less, preferably 40 ms or less, more preferably 30 ms or less, more preferably 20 ms or less, more preferably 15 ms or less, more preferably 8 ms or less, more preferably 6 ms or less, more preferably 1 ms or less, more preferably 0.5 ms; and / or

[0557] iii) wherein the plasma pulse duration PD2 is 0.1 ms or more, preferably 0.2 ms or more, more preferably 0.3 ms or more, and even more preferably 0.5 ms or more; and / or

[0558] iv) Irradiation is performed by a microwave generator, preferably wherein the radiation has a frequency of 300 MHz to 300 GHz, more preferably 600 MHz to 100 GHz, more preferably 800 MHz to 10 GHz, more preferably 900 MHz to 3 GHz, and more preferably 2.45 GHz; and / or

[0559] v) Wherein the input power IP2, preferably the input power IP2 of the microwave generator, is 1000W to 10000W, more preferably 2500W to 8000W, more preferably 4000W to 8000W, more preferably 5000W to 7000W, more preferably 5000W to 6500W, and more preferably 5250W to 5750W; and / or

[0560] vi) Precursor P2 includes argon, oxygen, and / or nitrogen, preferably oxygen, and more preferably air; and / or

[0561] vii) wherein the precursor P2 comprises elements N (e.g., N2) and / or O (e.g., O2), preferably composed thereof; preferably comprises N2 and O2, preferably composed thereof; more preferably comprises O2, preferably composed thereof; and / or

[0562] viii) The pulse pause PP2 between two pulses is 1 μs or more, preferably 10 μs or more, more preferably 1 μs to 5 s, more preferably 0.1 ms to 10 ms, more preferably 0.5 ms to 2.0 ms, more preferably 1.5 ms to 2.0 ms, and more preferably 1.8 ms; and / or

[0563] ix) The total irradiation time TT2 is 0.1 seconds or more, preferably 1 second or more, more preferably 1 second to 5 minutes, and more preferably 5 seconds to 15 seconds; and / or

[0564] x) The ratio [ms / ms] of the total pulse duration PD2 [ms] to the total pulse pause PP2 [ms] is 0.05 or more, preferably 0.1 or more, more preferably 0.15 to 5, and even more preferably 0.2 to 0.5; and / or

[0565] xi) wherein the process pressure PR2 is from 0.01 mbar to 500 mbar, preferably from 0.1 mbar to 100 mbar, more preferably from 0.5 mbar to 10 mbar, more preferably from 0.8 mbar to 6.0 mbar, and even more preferably from 1.0 mbar to 4.0 mbar; and / or

[0566] xii) Wherein the process temperature PT2 increases during plasma pretreatment, preferably increasing steadily; and / or

[0567] xiii) wherein the process temperature PT2 is at least partially, preferably at least 220°C, more preferably at least 240°C, more preferably at least 250°C, more preferably at least 255°C, or more preferably at least 270°C, more preferably at least 280°C, at the end of the plasma pretreatment process; and / or

[0568] xiv) wherein the flow rate of precursor P2 is 0.1 to 500 sccm, preferably 5 to 100 sccm, more preferably 8 to 50 sccm, and even more preferably 20 to 30 sccm.

[0569] According to the method described in any one of the foregoing schemes,

[0570] The corona pretreatment includes the following steps:

[0571] Position at least a portion of the glass surface of the glass element between the first and second electrodes;

[0572] The precursor P3 surrounds at least a portion of the glass surface of the glass element; and

[0573] A voltage V1 is applied between the first and second electrodes;

[0574] The following parameters must be satisfied, preferably all of them:

[0575] The first electrode is made of brass; and / or

[0576] ii) The second electrode is made of aluminum; and / or

[0577] iii) Precursor P3 is selected from oxygen, nitrogen, air and / or mixtures thereof; and / or

[0578] iv) The process pressure PR3 is 100 mbar to 2000 mbar, preferably 500 mbar to 1500 mbar, more preferably 900 mbar to 1200 mbar; and / or

[0579] v) The voltage V1 is applied for a period of 0.1 s to 30 s, preferably 0.5 s to 5 s; and / or

[0580] vi) The voltage V1 is from 1kV to 10kV, preferably from 2kV to 5kV; and / or

[0581] vii) The frequency of voltage V1 is 1 to 50 kHz, preferably 10 to 30 kHz, and more preferably 12 to 18 kHz.

[0582] According to any one of the foregoing schemes, the pretreatment process is performed before the coating process.

[0583] According to any one of the foregoing schemes, the time between the pretreatment process and the coating process is less than one year, preferably less than six months, more preferably less than one day, more preferably less than one hour, more preferably less than one minute, more preferably less than 30 seconds, more preferably less than 20 seconds, and more preferably less than 15 seconds; and / or

[0584] The duration is 1 second or more, preferably 3 seconds or more, more preferably 8 seconds or more, and even more preferably 10 seconds or more.

[0585] The method according to any one of the foregoing schemes includes the following steps:

[0586] Post-processing is performed on at least a portion of the glass surface of the glass element, wherein the post-processing includes the following steps:

[0587] At least a portion of the glass surface of the glass element is surrounded by a precursor P4 containing argon, oxygen and / or nitrogen, preferably argon and / or oxygen; and the glass element is preferably cooled in the presence of the precursor P4, more preferably cooled to room temperature.

[0588] According to any one of the foregoing schemes, the method wherein post-treatment is performed after the coating process.

[0589] A pretreated glass element, preferably obtained by the method according to any one of the foregoing embodiments,

[0590] At least a portion of the glass surface of the glass element satisfies one or more of the following parameters:

[0591] The ratio of the polar portion of surface energy [mN / m] to the dispersive portion of surface energy [mN / m] is 1.4 or less, preferably 0.10 to 1.44, more preferably 0.50 to 1.40, and more preferably 1.00 to 1.35; and / or

[0592] ii) The polar portion of the surface energy is 39.50 mN / m or less, preferably 20.00 mN / m to 39.50 mN / m, more preferably 36.00 to 38.50 mN / m, and even more preferably 36.50 to 38.00 mN / m; and / or

[0593] iii) The surface energy of the dispersive portion is 27.5 mN / m or more, preferably 27.50 mN / m to 40.00 mN / m, more preferably 28.00 mN / m to 35.00 mN / m, and more preferably 29.00 mN / m to 32.50 mN / m.

[0594] The use of the pretreated glass element according to any one of the foregoing schemes in a method including a coating process, preferably wherein the coating process includes a CVD process, more preferably a PECVD, PICVD or PACVD process, and more preferably a PICVD process.

[0595] Use of a glass element pretreated according to any of the foregoing items in a method according to any one of the following schemes.

[0596] A coated glass element including a glass surface,

[0597] The glass element is a container, preferably a pharmaceutical glass container;

[0598] At least a portion of the glass surface is coated;

[0599] The coating comprises at least one layer;

[0600] The coated glass containers must meet the following parameters:

[0601] After alkali treatment, the leaching amount of [Na] ions is less than 10 mg / L.

[0602] The coated glass element according to any one of the foregoing solutions,

[0603] The coated glass containers must meet the following parameters:

[0604] The leaching amount of [Na] ions after heat treatment and alkali treatment is less than 10 mg / L.

[0605] The coated glass element according to any one of the foregoing solutions,

[0606] After alkali treatment, preferably after heat treatment and alkali treatment, the leaching amount of [Na] ions is less than 9 mg / L, preferably less than 7 mg / L, more preferably less than 5 mg / L, more preferably less than 4 mg / L, more preferably less than 3 mg / L, more preferably less than 2 mg / L, more preferably less than 1 mg / L, more preferably less than 0.7 mg / L, more preferably less than 0.3 mg / L, more preferably less than 0.2 mg / L, and more preferably less than 0.1 mg / L.

[0607] The coated glass element according to any one of the foregoing solutions,

[0608] After alkali treatment, preferably after heat treatment and alkali treatment, the leaching amount of [Na] ions is 0 mg / L or more, preferably 0.001 mg / L or more, more preferably 0.01 mg / L or more, and even more preferably 0.1 mg / L or more.

[0609] A coated glass element, preferably a coated glass element according to any of the foregoing embodiments, includes a glass surface.

[0610] The glass element is a container, preferably a pharmaceutical glass container;

[0611] At least a portion of the glass surface is coated;

[0612] The coating comprises at least one layer;

[0613] The leaching amount of [Na] ions after alkali treatment, preferably after heat treatment and alkali treatment, is a;

[0614] Where a ≤ b*c;

[0615] If 0.9 x (full volume) of the container is ≤ 1 ml, then b is 5.00 mg / l;

[0616] If the container's 0.9 x (full volume) > 1 ml and ≤ 2 ml, then b is 4.50 mg / l;

[0617] If the container's 0.9 x (full volume) > 2 ml and ≤ 3 ml, then b is 4.10 mg / l;

[0618] If the container's 0.9 x (full volume) > 3 ml and ≤ 5 ml, then b is 3.20 mg / l;

[0619] Wherein, if the container's 0.9 x (full volume) > 5 ml and ≤ 10 ml, then b is 2.50 mg / l;

[0620] Wherein, if 0.9 x (full volume) of the container is greater than 10 ml and less than or equal to 20 ml, then b is 2.00 mg / l;

[0621] Wherein, if the container's 0.9 x (full volume) > 20 ml and ≤ 50 ml, then b is 1.50 mg / l;

[0622] Wherein, if 0.9 x (full volume) of the container is greater than 50 ml and less than or equal to 100 ml, then b is 1.20 mg / l;

[0623] Wherein, if 0.9 x (full volume) of the container is greater than 100 ml and less than or equal to 200 ml, then b is 1.00 mg / l;

[0624] Where, if 0.9 x (full volume) of the container > 200 ml and ≤ 500 ml, then b is 0.75 mg / l; and

[0625] Wherein, if 0.9 x (full volume) of the container > 500 ml, then b is 0.50 mg / l; and

[0626] Wherein c is 1.00, preferably 0.90, more preferably 0.80, more preferably 0.70, more preferably 0.60, more preferably 0.50, more preferably 0.40, more preferably 0.30, more preferably 0.20, more preferably 0.15, more preferably 0.10, more preferably 0.08, and more preferably 0.05.

[0627] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0628] The glass element is a container, preferably a pharmaceutical glass container;

[0629] At least a portion of the glass surface is coated;

[0630] The coating comprises at least one layer;

[0631] The coated glass containers must meet the following parameters:

[0632] The leaching amounts [mg / l] of [Si], [B], [Al] and / or [Ca] ions after 3 years of storage at pH 8 are:

[0633] [Si] ions at concentrations of 25 mg / L or less, preferably 3.7 mg / L or less, more preferably 1.0 to 3.0 mg / L; and / or, preferably and,

[0634] [B] ions at concentrations of 1.0 mg / L or less, preferably 0.5 mg / L or less, more preferably 0.001 to 0.2 mg / L; and / or, preferably, and

[0635] [Al] ions at concentrations of 1.0 mg / L or less, preferably 0.5 mg / L or less, more preferably 0.001 to 0.14 mg / L; and / or, preferably, and

[0636] [Ca] ions at concentrations of 10 mg / L or less, preferably 5 mg / L or less, and more preferably 1.0 to 4.9 mg / L.

[0637] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0638] The glass element is a container, preferably a pharmaceutical glass container;

[0639] At least a portion of the glass surface is coated;

[0640] The coating comprises at least one layer;

[0641] The coated glass containers must meet the following parameters:

[0642] The leaching amount [mg / l] of [Si], [B], [Al] and / or [Ca] ions after 3 years of storage at pH 5.5 is:

[0643] [Si] ions at concentrations of 1.30 mg / L or less, preferably 1.10 mg / L or less, more preferably 0.001 to 0.60 mg / L; and / or, preferably and,

[0644] [B] ions at concentrations of 0.1 mg / L or less, preferably 0.05 mg / L or less, more preferably 0.001 to 0.004 mg / L; and / or, preferably, and

[0645] [Al] ions at concentrations of 0.1 mg / L or less, preferably 0.01 mg / L or less, more preferably 0.001 to 0.0004 mg / L; and / or, preferably and,

[0646] [Ca] ions at concentrations of 0.1 mg / L or less, preferably 0.05 mg / L or less, and more preferably 0.001 to 0.004 mg / L.

[0647] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0648] At least a portion of the glass surface is coated;

[0649] The coating comprises at least one layer;

[0650] At least one layer of the coating satisfies the following parameters:

[0651] [Al + ] 80 / [Al + ] 20 ≥ 1.8;

[0652] Among them [Al + ] 20 [Al] is measured by TOF-SIMS at 20% of the time required for the sputtering gun to reach the glass surface. + ] Ion counting; and

[0653] Among them [Al + ] 80 [Al] is measured by TOF-SIMS at 80% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

[0654] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0655] At least a portion of the glass surface is coated;

[0656] The coating comprises at least one layer;

[0657] At least one layer of the coating satisfies the following parameters:

[0658] [Al +] 80 / [Al + ] 20 ≥ x1 [Al+] ;

[0659] Where x1 [Al+] The value is 2.0, preferably 3, more preferably 5, more preferably 7, more preferably 10, more preferably 15, more preferably 20, more preferably 25; and / or

[0660] [Al + ] 80 / [Al + ] 20 ≤ x2 [Al+] ;

[0661] Where x2 [Al+] The value is 500, preferably 200, preferably 100, more preferably 50, more preferably 40, more preferably 35, more preferably 30, more preferably 29, and more preferably 28.

[0662] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0663] At least a portion of the glass surface is coated;

[0664] The coating comprises at least one layer;

[0665] At least one layer of the coating satisfies the following parameters:

[0666] y1 [Al+] ≤ [Al + ] 80 / [Al + ] 60 ≤ y2 [Al+] ;

[0667] y1 [Al+] ≤ [Al + ] 60 / [Al + ] 40 ≤ y2 [Al+] ; and / or

[0668] y1 [Al+] ≤ [Al + ] 40 / [Al + ] 20 ≤ y2 [Al+] ;

[0669] Where y1 [Al+]The value is 1.01, preferably 2, more preferably 3, more preferably 5, more preferably 10, more preferably 15, more preferably 20, more preferably 25; and / or

[0670] Where y2 [Al+] The value is 500, preferably 200, preferably 100, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5; and

[0671] Among them [Al + ] 40 [Al] is measured by TOF-SIMS at 40% of the time required for the sputtering gun beam to reach the glass surface. + ] Ion counting; and

[0672] Among them [Al + ] 60 [Al] is measured by TOF-SIMS at 60% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

[0673] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0674] At least a portion of the glass surface is coated;

[0675] The coating comprises at least one layer;

[0676] At least one layer of the coating satisfies the following parameters:

[0677] [SiCH3 + ] 20 / [SiCH3 + ] 80 ≥ x1 [SiCH3+] ;

[0678] Where x1 [SiCH3+] The value is 1.05, preferably 1.1, more preferably 1.2, more preferably 1.4, more preferably 1.6, more preferably 1.7, and more preferably 1.8; and / or

[0679] [SiCH3 + ] 20 / [SiCH3 + ] 80 ≤ x2 [SiCH3+] ;

[0680] Where x2 [SiCH3+]The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2, and more preferably 1.8; and

[0681] Among them [SiCH3 + ] 20 The [SiCH3] value at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting; and

[0682] Among them [SiCH3 + ] 80 The [SiCH3] value is measured by TOF-SIMS at 80% of the time required for the sputtering torch beam to reach the glass surface. + Ion counting.

[0683] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0684] At least a portion of the glass surface is coated;

[0685] The coating comprises at least one layer;

[0686] At least one layer of the coating satisfies the following parameters:

[0687] y1 [SiCH3+] ≤ [SiCH3 + ] 20 / [SiCH3 + ] 40 ≤ y2 [SiCH3+] ;

[0688] y1 [SiCH3+] ≤ [SiCH3 + ] 40 / [SiCH3 + ] 60 ≤ y2 [SiCH3+] ; and / or

[0689] y1 [SiCH3+] ≤ [SiCH3 + ] 60 / [SiCH3 + ] 80 ≤ y2 [SiCH3+] ;

[0690] Where y1 [SiCH3+] The value is 1.0, preferably 1.1, more preferably 1.2, even more preferably 1.4, and even more preferably 1.5; and / or

[0691] Where y2 [SiCH3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2, and more preferably 1.5; and

[0692] Among them [SiCH3 + ] 20 The [SiCH3] value at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting;

[0693] Among them [SiCH3 + ] 40 The [SiCH3] value at 40% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting;

[0694] Among them [SiCH3 + ] 60 The [SiCH3] value at 60% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. + ] Ion counting; and

[0695] Among them [SiCH3 + ] 80 The [SiCH3] value is measured by TOF-SIMS at 80% of the time required for the sputtering torch beam to reach the glass surface. + Ion counting.

[0696] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0697] At least a portion of the glass surface is coated;

[0698] The coating comprises at least one layer;

[0699] At least one layer of the coating satisfies the following parameters:

[0700] [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 80 ≥ x1 [Si3C5H15O3+] ;

[0701] Where x1 [Si3C5H15O3+] The value is 1.2, preferably 2, more preferably 3, more preferably 5, and even more preferably 8; and / or

[0702] [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 80 ≤ x2 [Si3C5H15O3+] ;

[0703] Where x2 [Si3C5H15O3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 15, more preferably 12, more preferably 10, more preferably 9; and

[0704] Among them, [Si3C5H] 15 O3 + ] 20 The value of [Si3C5H] at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting; and / or

[0705] Among them, [Si3C5H] 15 O3 + ] 80 The value of [Si3C5H] at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + Ion counting.

[0706] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0707] At least a portion of the glass surface is coated;

[0708] The coating comprises at least one layer;

[0709] At least one layer of the coating satisfies the following parameters:

[0710] y1 [Si3C5H15O3+] ≤ [Si3C5H 15 O3 + ] 20 / [Si3C5H 15 O3 + ] 40 ≤ y2 [Si3C5H15O3+] ;

[0711] y1 [Si3C5H15O3+] ≤ [Si3C5H 15 O3 + ]40 / [Si3C5H 15 O3 + ] 60 ≤ y2 [Si3C5H15O3+] ; and / or

[0712] y1 [Si3C5H15O3+] ≤ [Si3C5H 15 O3 + ] 60 / [Si3C5H 15 O3 + ] 80 ≤ y2 [Si3C5H15O3+] ;

[0713] Where y1 [Si3C5H15O3+] The value is 1.0, preferably 1.1, more preferably 1.5, more preferably 2, and even more preferably 2.0; and / or

[0714] Where y2 [Si3C5H15O3+] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 2, and more preferably 1.5; and

[0715] Among them, [Si3C5H] 15 O3 + ] 20 The value of [Si3C5H] at 20% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting;

[0716] Among them, [Si3C5H] 15 O3 + ] 40 The value of [Si3C5H] at 40% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting;

[0717] Among them, [Si3C5H] 15 O3 + ] 60 The value of [Si3C5H] at 60% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + ] Ion counting; and

[0718] Among them, [Si3C5H] 15 O3 + ] 80The value of [Si3C5H] at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. 15 O3 + Ion counting.

[0719] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0720] At least a portion of the glass surface is coated;

[0721] The coating comprises at least one layer;

[0722] At least one layer of the coating satisfies the following parameters:

[0723] [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≥ 1.0;

[0724] Among them, [Si2C5H] 15 O2 - ] 20 The value of [Si2C5H] at 20% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - ] Ion counting; and

[0725] Among them, [Si2C5H] 15 O2 - ] 80 The value of [Si2C5H] at 80% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - Ion counting.

[0726] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0727] At least a portion of the glass surface is coated;

[0728] The coating comprises at least one layer;

[0729] At least one layer of the coating satisfies the following parameters:

[0730] [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2- ] 80 ≥ x1 [Si2C5H15O2-] ;

[0731] Where x1 [Si2C5H15O2-] The value is 1.2, preferably 1.5, more preferably 2, more preferably 3, more preferably 5, more preferably 8, and more preferably 12; and / or

[0732] [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≤ x2 [Si2C5H15O2-] ;

[0733] Where x2 [Si2C5H15O2-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 25, more preferably 20, more preferably 18, more preferably 15, and more preferably 14.

[0734] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0735] At least a portion of the glass surface is coated;

[0736] The coating comprises at least one layer;

[0737] At least one layer of the coating satisfies the following parameters:

[0738] z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 40 ≤ z2 [Si2C5H15O2-] ;

[0739] z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 40 / [Si2C5H 15 O2 - ] 60 ≤ z2 [Si2C5H15O2-] ; and / or

[0740] z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 60 / [Si2C5H 15 O2 - ] 80 ≤ z2 [Si2C5H15O2-] ;

[0741] z1 [Si2C5H15O2-] The value is 1.0, preferably 1.1, more preferably 1.4, more preferably 1.5, more preferably 1.6, more preferably 2.0; more preferably 2.4; and / or

[0742] Where z2 [Si2C5H15O2-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 3, more preferably 2, more preferably 1.5; and

[0743] Among them, [Si2C5H] 15 O2 - ] 40 The value of [Si2C5H] at 40% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - ] Ion counting; and

[0744] Among them, [Si2C5H] 15 O2 - ] 60 The value of [Si2C5H] at 60% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - Ion counting.

[0745] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0746] At least a portion of the glass surface is coated;

[0747] The coating comprises at least one layer;

[0748] At least one layer of the coating satisfies the following parameters:

[0749] [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 80 ≥ x1 [Si2C3H9O3-] ;

[0750] Where x1 [Si2C3H9O3-] The value is 1.1, preferably 1.5, more preferably 2, and even more preferably 3; and / or

[0751] [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 80 ≤ x2 [Si2C3H9O3-] ;

[0752] Where x2 [Si2C3H9O3-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 8, more preferably 6, more preferably 5, more preferably 4; and

[0753] Among them, [Si2C3H9O3] - ] 20 The Si2C3H9O3 content at 20% of the time required for the sputtering torch beam to reach the glass surface was measured using TOF-SIMS. - ] Ion counting; and

[0754] Among them, [Si2C3H9O3] - ] 80 The [Si2C3H9O3] value at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - Ion counting.

[0755] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0756] At least a portion of the glass surface is coated;

[0757] The coating comprises at least one layer;

[0758] At least one layer of the coating satisfies the following parameters:

[0759] x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 40 ≤ x2 [Si2C3H9O3-] ;

[0760] x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 40 / [Si2C3H9O3 - ] 60 ≤ x2 [Si2C3H9O3-] ; and / or

[0761] x1 [Si2C3H9O3-] ≤ [Si2C3H9O3- ] 60 / [Si2C3H9O3 - ] 80 ≤ x2 [Si2C3H9O3-] ;and

[0762] Where x1 [Si2C3H9O3-] The value is 1.05, preferably 1.1, more preferably 1.5, more preferably 2, and even more preferably 3; and / or

[0763] Where x2 [Si2C3H9O3-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 3, more preferably 2, more preferably 1.5; and

[0764] Among them, [Si2C3H9O3] - ] 20 The [Si2C3H9O3] value at 20% of the time required for the sputtering torch beam to reach the glass surface was measured using TOF-SIMS. - ] Ion counting;

[0765] Among them, [Si2C3H9O3] - ] 40 The [Si2C3H9O3] value at 40% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - ] Ion counting;

[0766] Among them, [Si2C3H9O3] - ] 60 The [Si2C3H9O3] value at 60% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - ] Ion counting; and

[0767] Among them, [Si2C3H9O3] - ] 80 The [Si2C3H9O3] value at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - Ion counting.

[0768] A coated glass element, preferably according to any one of the foregoing embodiments, includes a glass surface.

[0769] At least a portion of the glass surface is coated;

[0770] The coating comprises at least one layer;

[0771] At least one layer of the coating satisfies the following parameters:

[0772] [AlO2 - ] 90 / [AlO2 - ] 20 ≥ x1 [AlO2-] ;

[0773] Where x1 [AlO2-] The value is 1.3, preferably 1.5, more preferably 1.8, and even more preferably 2.0; and / or

[0774] [AlO2 - ] 90 / [AlO2 - ] 20 ≤ x2 [AlO2-] ;

[0775] Where x2 [AlO2-] The value is 100, preferably 75, more preferably 50, more preferably 40, more preferably 30, more preferably 20, more preferably 10, more preferably 5, more preferably 3, more preferably 2, more preferably 1.5; and

[0776] Among them [AlO2] - ] 20 [AlO2] was measured by TOF-SIMS at 20% of the time required for the sputtering gun beam to reach the glass surface. - ] Ion counting; and

[0777] Among them [AlO2] - ] 90 [AlO2] was measured by TOF-SIMS at 90% of the time required for the sputtering gun beam to reach the glass surface. - Ion counting.

[0778] The coated glass element according to any one of the foregoing solutions,

[0779] The at least one layer includes the elements Si, O, and C, as measured by XPS.

[0780] The coated glass element according to any one of the foregoing solutions,

[0781] The at least one layer comprises SiO2 as measured by XPS. x C y ;

[0782] Where x is 0.3 to 3.0, preferably 0.5 to 2.0, more preferably 0.9 to 1.5; and / or

[0783] Wherein y is 0 to 6.0, preferably 0.5 to 4.0, and more preferably 2.5 to 3.5.

[0784] The coated glass element according to any one of the foregoing solutions,

[0785] The thickness of the coating is 1 nm to 1 mm, preferably 10 nm to 0.5 mm; more preferably 20 nm to 100 nm.

[0786] The coated glass element according to any one of the foregoing solutions,

[0787] The at least one layer can be obtained by a CVD process, preferably PECVD, PICVD or PACVD, and more preferably PICVD.

[0788] The coated glass element according to any one of the foregoing solutions,

[0789] The at least one layer can be obtained by the method according to any one of the foregoing schemes.

[0790] The coated glass element according to any one of the foregoing solutions,

[0791] The coating consists of at least one layer; and / or

[0792] The coating may be obtained through a coating process; and / or

[0793] The coating is a single-layer coating.

[0794] The coated glass element according to any one of the foregoing solutions,

[0795] At least one of these layers is in direct contact with the glass surface of the glass element and / or the glass surface of the pretreated glass element.

[0796] The coated glass element according to any one of the foregoing solutions,

[0797] Where at least one layer is the outermost layer; and / or

[0798] The coating faces the inner cavity of the glass element.

[0799] The coated glass element according to any one of the foregoing solutions,

[0800] The coating is a multi-layer coating.

[0801] A sealed coated glass element, comprising:

[0802] The coated glass element according to any one of the foregoing schemes; and

[0803] A closed system, preferably with a stopper and / or a cap, more preferably with a stopper and a cap.

[0804] A sealed coated glass element, comprising:

[0805] The coated glass element according to any one of the foregoing schemes; and

[0806] plunger and / or plunger rod; and / or

[0807] A closed system, preferably a tip cap and / or needle shield.

[0808] The closed-coated glass element according to any one of the foregoing solutions,

[0809] The sealed coated glass element passed the container closure integrity test according to DIN EN ISO 8871-5:2016; Chapter 4.4 in conjunction with Annex D.

[0810] A filled coated glass element, comprising:

[0811] The coated glass element according to any one of the foregoing schemes; and

[0812] The composition, preferably a pharmaceutical composition, more preferably a composition containing a biological product or mRNA.

[0813] The coated glass element according to any one of the foregoing solutions,

[0814] The time required for the sputtering gun to reach the glass surface is 0.5 to 60 minutes, preferably 1 to 10 minutes, and more preferably 2 to 4 minutes; and / or

[0815] In the case of measuring positive ions, the point at which the sputtering gun reaches the glass surface is [Al]. + ] Ion counting and [Si + The point at which the ratio of ion counts equals or first exceeds the value of 0.10; and / or

[0816] In the case of measuring negative ions, the point at which the sputtering gun reaches the glass surface is [AlO2]. - ] Ion counting and [Si - The point at which the ratio of ion counts equals or first exceeds the value of 0.10; and / or

[0817] Among the ion counting, the preferred ion is [AlO2]. - [Si2C3H9O3] - [Si2C5H] 15 O2 - [Si3C5H] 15 O3 + ]、[Al + ] and / or [SiCH3 + The count can be obtained using the method described in the instruction manual.

[0818] The method, use, glass element, coated glass element and / or filled coated glass element according to any one of the foregoing embodiments, wherein the glass is borosilicate glass, aluminosilicate glass, lithium-aluminosilicate (LAS) glass, preferably borosilicate glass.

[0819] According to any one of the foregoing embodiments, the method, use, glass element, coated glass element, and / or filled coated glass element, wherein the composition of the glass, in mass percent, comprises:

[0820] SiO2: 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%; and / or

[0821] B2O3: 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%; and / or

[0822] Al2O3: 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%; and / or

[0823] X₂O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, and Li, preferably X is Na and / or K; and / or

[0824] YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg.

[0825] According to any one of the foregoing embodiments, the method, use, glass element, coated glass element, and / or filled coated glass element, wherein the composition of the glass, in mass percent, comprises the following:

[0826] SiO2: 30 to 98%, preferably 50 to 90%, more preferably 70.0 to 74.0%;

[0827] B2O3: 0 to 30%, preferably 3 to 20%, more preferably 7.0 to 16.0%;

[0828] Al2O3: 0 to 30%, preferably 1 to 15%, more preferably 3.0 to 6.5%;

[0829] X2O: 0 to 30%, preferably 1 to 15%, more preferably 2.0 to 7.2%, wherein X is selected from Na, K, and Li, and preferably X is Na and / or K;

[0830] YO: 0 to 30%, preferably 0.1 to 5%, more preferably 0.5 to 1.0%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg; and

[0831] Preferably remove unavoidable impurities.

[0832] According to any one of the foregoing embodiments, the method, use, glass element, coated glass element, and / or filled coated glass element, wherein the composition of the glass, in mass percent, comprises the following:

[0833] SiO2: 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%; and / or

[0834] B2O3: 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%; and / or

[0835] Al2O3: 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%; and / or

[0836] X₂O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, and Li, preferably X is Na and / or K; and / or

[0837] YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg.

[0838] According to any one of the foregoing embodiments, the method, use, glass element, coated glass element, and / or filled coated glass element, wherein the composition of the glass, in mass percent, comprises the following:

[0839] SiO2: 20 to 98%, preferably 40 to 75%, more preferably 50 to 65%;

[0840] B2O3: 0 to 30%, preferably 1 to 15%, more preferably 3 to 9%;

[0841] Al2O3: 0 to 30%, preferably 10 to 20%, more preferably 13 to 18%;

[0842] X2O: 0 to 30%, preferably 0 to 5%, more preferably 0 to 3%, wherein X is selected from Na, K, and Li, and preferably X is Na and / or K;

[0843] YO: 0 to 50%, preferably 0.1 to 40%, more preferably 10 to 35%, wherein Y is selected from Ca, Mg, Ba, and preferably Y is Ca and / or Mg; and

[0844] Preferably remove unavoidable impurities.

[0845] According to any one of the foregoing schemes, the method, use, glass element, coated glass element, and / or filled coated glass element,

[0846] The glass element therein is a container, more preferably a drug container, more preferably a vial, syringe, ampoule or cartridge, and more preferably a vial.

[0847] According to any one of the foregoing schemes, the method, use, glass element, coated glass element, and / or filled coated glass element,

[0848] The full volume of the container is 0.1 ml to 1000 ml, preferably 0.5 ml to 500 ml, more preferably 1 ml to 250 ml, more preferably 2 ml to 30 ml, more preferably 2 ml to 15 ml, more preferably about 1 ml, 2 ml, 3 ml, 4 ml, 5 ml, 6 ml, 7 ml, 8 ml, 9 ml, 10 ml, 11 ml, 12 ml, 13 ml, 14 ml or 15 ml; more preferably 5 ml to 15 ml.

[0849] According to any one of the foregoing schemes, the method, use, glass element, coated glass element, and / or filled coated glass element,

[0850] Preferably, the glass element is a tube or a container, more preferably a container;

[0851] The glass element includes an inner surface, wherein the inner surface includes at least a portion of the glass surface, preferably at least a portion of the glass surface.

[0852] According to any one of the foregoing schemes, the method, use, glass element, coated glass element, and / or filled coated glass element,

[0853] Preferably, the glass element is a tube or a container, more preferably a container;

[0854] The glass element includes an outer surface, and the outer surface includes at least a portion of the glass surface, preferably at least a portion of the glass surface.

[0855] According to any one of the foregoing embodiments, the method, application, glass element, coated glass element, and / or filler-type coated glass element,

[0856] The glass element is a vial or cartridge comprising a cylindrical portion, a neck, and a crown, wherein at least the inner surface of the cylindrical portion is coated.

[0857] According to any one of the foregoing schemes, the method, use, glass element, coated glass element, and / or filled coated glass element,

[0858] The container has at least a portion of its glass surface, which includes at least a portion of its inner surface. Preferably, the at least portion of the glass surface is the surface in contact with the liquid when the container is stably placed on the ground and filled with liquid, wherein the liquid volume is 10% or more, preferably 30% or more, and more preferably 90% or more, relative to the full volume of the container [vol. / vol.].

[0859] According to any one of the foregoing schemes, the method, use, glass element, coated glass element, and / or filled coated glass element,

[0860] The glass element is a vial or cartridge comprising a cylindrical portion, a neck, and a crown, wherein the crown, preferably, and the neck, are uncoated; and / or

[0861] The glass element is a syringe, comprising a flange, a cylindrical portion, and a tip, preferably a needle, wherein the needle, preferably the flange, more preferably the tip, has no coating.

[0862] List of reference numerals

[0863] glass surface

[0864] coating

[0865] Pre-treatment of glass surfaces

[0866] 1001 Preprocessing

[0867] 1002 coating process

[0868] 1003 Post-processing

Claims

1. A coated glass element comprising a glass surface, At least a portion of the glass surface is coated with a coating. The coating comprises at least one layer; At least one layer of the coating satisfies the following parameters: [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≥ 1.0; where [Si2C5H 15 O2 - ] 20 is the count of [Si2C5H 15 O2 - ] ions measured by TOF-SIMS at 20% of the time required for the sputter gun beam to reach the glass surface; as well as Among them, [Si2C5H] 15 O2 - ] 80 The [Si2C5H] value measured by TOF-SIMS at 80% of the time required for the sputtering gun beam to reach the glass surface. 15 O2 - ] Ion counting, and In the case of measuring positive ions, the point at which the sputtering gun beam reaches the glass surface is [Al]. + ] Ion counting and [Si + The point at which the ratio of ion counts equals or first exceeds the value of 0.10; and / or In the case of measuring negative ions, the point at which the sputtering gun beam reaches the glass surface is [AlO2]. - ] Ion counting and [Si - The ratio of ion counts equals or first exceeds the value of 0.10 at the point when it is equal to or first exceeds the value of 0.

10. During the coating process, the process temperature PT1 is between 320°C and 500°C; and the irradiation pulse duration PD1 is less than 50 µs.

2. The coated glass element according to claim 1, wherein at least one layer of the coating satisfies the following parameters: [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≥ x1 [Si2C5H15O2-] ;where x1 [Si2C5H15O2-] 1.2; and / or [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 80 ≤ x2 [Si2C5H15O2-] ;where x2 [Si2C5H15O2-] It is 100.

3. The coated glass element according to claim 2, wherein x1 [Si2C5H15O2-] 1.5; and / or Where x2 [Si2C5H15O2-] It is 75.

4. The coated glass element according to claim 2, wherein x1 [Si2C5H15O2-] For 2; and / or Where x2 [Si2C5H15O2-] It is 50.

5. The coated glass element according to claim 2, wherein x1 [Si2C5H15O2-] For 3; and / or Where x2 [Si2C5H15O2-] It is 40.

6. The coated glass element according to claim 2, wherein x1 [Si2C5H15O2-] 5; and / or Where x2 [Si2C5H15O2-] It is 30.

7. The coated glass element according to claim 2, wherein x1 [Si2C5H15O2-] For 8; and / or Where x2 [Si2C5H15O2-] It is 25.

8. The coated glass element according to claim 2, wherein x1 [Si2C5H15O2-] 12; and / or Where x2 [Si2C5H15O2-] It is 20.

9. The coated glass element according to claim 2, wherein x2 [Si2C5H15O2-] It is 18.

10. The coated glass element according to claim 2, wherein x2 [Si2C5H15O2-] It is 15.

11. The coated glass element according to claim 2, wherein x2 [Si2C5H15O2-] It is 14.

12. The coated glass element according to any one of claims 1 to 11, At least one layer of the coating satisfies the following parameters: z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 20 / [Si2C5H 15 O2 - ] 40 ≤ z2 [Si2C5H15O2-] ; z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 40 / [Si2C5H 15 O2 - ] 60 ≤ z2 [Si2C5H15O2-] ; and / or z1 [Si2C5H15O2-] ≤ [Si2C5H 15 O2 - ] 60 / [Si2C5H 15 O2 - ] 80 ≤ z2 [Si2C5H15O2-] ; z1 [Si2C5H15O2-] 1.0; and / or Where z2 [Si2C5H15O2-] It is 100; and Among them, [Si2C5H] 15 O2 - ] 40 The value of [Si2C5H] at 40% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - ] Ion counting; and Among them, [Si2C5H] 15 O2 - ] 60 The value of [Si2C5H] at 60% of the time required for the sputtering torch beam to reach the glass surface, as measured by TOF-SIMS. 15 O2 - Ion counting.

13. The coated glass element according to claim 12, wherein z1 [Si2C5H15O2-] 1.1; and / or Where z2 [Si2C5H15O2-] It is 75.

14. The coated glass element according to claim 12, wherein z1 [Si2C5H15O2-] 1.4; and / or Where z2 [Si2C5H15O2-] It is 50.

15. The coated glass element according to claim 12, wherein z1 [Si2C5H15O2-] 1.5; and / or Where z2 [Si2C5H15O2-] It is 40.

16. The coated glass element according to claim 12, wherein z1 [Si2C5H15O2-] 1.6; and / or Where z2 [Si2C5H15O2-] It is 30.

17. The coated glass element according to claim 12, wherein z1 [Si2C5H15O2-] 2.0; and / or Where z2 [Si2C5H15O2-] It is 20.

18. The coated glass element according to claim 12, wherein z1 [Si2C5H15O2-] 2.4; and / or Where z2 [Si2C5H15O2-] It is 10.

19. The coated glass element according to claim 12, wherein z2 [Si2C5H15O2-] It is 5.

20. The coated glass element according to claim 12, wherein z2 [Si2C5H15O2-] The value is 3.

21. The coated glass element according to claim 12, wherein z2 [Si2C5H15O2-] The value is 2.

22. The coated glass element according to claim 12, wherein z2 [Si2C5H15O2-] It is 1.

5.

23. The coated glass element according to any one of claims 1 to 11, At least one layer of the coating satisfies the following parameters: [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 80 ≥ x1 [Si2C3H9O3-] ; Where x1 [Si2C3H9O3-] 1.1; and / or [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 80 ≤ x2 [Si2C3H9O3-] ; Where x2 [Si2C3H9O3-] It is 100; and Among them, [Si2C3H9O3] - ] 20 The [Si2C3H9O3] value at 20% of the time required for the sputtering torch beam to reach the glass surface was measured using TOF-SIMS. - ] Ion counting; and Among them, [Si2C3H9O3] - ] 80 The [Si2C3H9O3] value at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - Ion counting.

24. The coated glass element according to claim 23, wherein x1 [Si2C3H9O3-] 1.5; and / or Where x2 [Si2C3H9O3-] It is 75.

25. The coated glass element according to claim 23, wherein x1 [Si2C3H9O3-] For 2; and / or Where x2 [Si2C3H9O3-] It is 50.

26. The coated glass element according to claim 23, wherein x1 [Si2C3H9O3-] For 3; and / or Where x2 [Si2C3H9O3-] It is 40.

27. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] It is 30.

28. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] It is 20.

29. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] It is 10.

30. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] It is 5.

31. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] The value is 3.

32. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] The value is 2.

33. The coated glass element according to claim 23, wherein x2 [Si2C3H9O3-] It is 1.

5.

34. The coated glass element according to any one of claims 1 to 11, At least one layer of the coating satisfies the following parameters: x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 20 / [Si2C3H9O3 - ] 40 ≤ x2 [Si2C3H9O3-] ; x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 40 / [Si2C3H9O3 - ] 60 ≤ x2 [Si2C3H9O3-] ; and / or x1 [Si2C3H9O3-] ≤ [Si2C3H9O3 - ] 60 / [Si2C3H9O3 - ] 80 ≤ x2 [Si2C3H9O3-] ; Where x1 [Si2C3H9O3-] 1.05; and / or Where x2 [Si2C3H9O3-] It is 100; and Among them, [Si2C3H9O3] - ] 20 The [Si2C3H9O3] value at 20% of the time required for the sputtering torch beam to reach the glass surface was measured using TOF-SIMS. - ] Ion counting; Among them, [Si2C3H9O3] - ] 40 The [Si2C3H9O3] value at 40% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - ] Ion counting; Among them, [Si2C3H9O3] - ] 60 The [Si2C3H9O3] value at 60% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - ] Ion counting; and Among them, [Si2C3H9O3] - ] 80 The [Si2C3H9O3] value at 80% of the time required for the sputtering gun beam to reach the glass surface, as measured by TOF-SIMS. - Ion counting.

35. The coated glass element according to claim 34, wherein x1 [Si2C3H9O3-] 1.1; and / or Where x2 [Si2C3H9O3-] It is 75.

36. The coated glass element according to claim 34, wherein x1 [Si2C3H9O3-] 1.5; and / or Where x2 [Si2C3H9O3-] It is 50.

37. The coated glass element according to claim 34, wherein x1 [Si2C3H9O3-] For 2; and / or Where x2 [Si2C3H9O3-] It is 40.

38. The coated glass element according to claim 34, wherein x1 [Si2C3H9O3-] For 3; and / or Where x2 [Si2C3H9O3-] It is 30.

39. The coated glass element according to claim 34, wherein x2 [Si2C3H9O3-] It is 20.

40. The coated glass element according to claim 34, wherein x2 [Si2C3H9O3-] It is 10.

41. The coated glass element according to claim 34, wherein x2 [Si2C3H9O3-] It is 5.

42. The coated glass element according to claim 34, wherein x2 [Si2C3H9O3-] The value is 3.

43. The coated glass element according to claim 34, wherein x2 [Si2C3H9O3-] The value is 2.

44. The coated glass element according to claim 34, wherein x2 [Si2C3H9O3-] It is 1.

5.

45. The coated glass element according to any one of claims 1 to 11, At least one layer of the coating satisfies the following parameters: [AlO2 - ] 90 / [AlO2 - ] 20 ≥ x1 [AlO2-] ; Where x1 [AlO2-] 1.3; and / or [AlO2 - ] 90 / [AlO2 - ] 20 ≤ x2 [AlO2-] ; Where x2 [AlO2-] It is 100; and Among them [AlO2] - ] 20 [AlO2] was measured by TOF-SIMS at 20% of the time required for the sputtering gun beam to reach the glass surface. - ] Ion counting; and Among them [AlO2] - ] 90 [AlO2] was measured by TOF-SIMS at 90% of the time required for the sputtering gun beam to reach the glass surface. - Ion counting.

46. ​​The coated glass element according to claim 45, wherein x1 [AlO2-] 1.5; and / or Where x2 [AlO2-] It is 75.

47. The coated glass element according to claim 45, wherein x1 [AlO2-] 1.8; and / or Where x2 [AlO2-] It is 50.

48. The coated glass element according to claim 45, wherein x1 [AlO2-] 2.0; and / or Where x2 [AlO2-] It is 40.

49. The coated glass element according to claim 45, wherein x2 [AlO2-] It is 30.

50. The coated glass element according to claim 45, wherein x2 [AlO2-] It is 20.

51. The coated glass element according to claim 45, wherein x2 [AlO2-] It is 10.

52. The coated glass element according to claim 45, wherein x2 [AlO2-] It is 5.

53. The coated glass element according to claim 45, wherein x2 [AlO2-] The value is 3.

54. The coated glass element according to claim 45, wherein x2 [AlO2-] The value is 2.

55. The coated glass element according to claim 45, wherein x2 [AlO2-] It is 1.

5.

56. A coated glass element according to any one of claims 1 to 55, At least one layer of the coating satisfies the following parameters: [Al + ] 80 / [Al + ] 20 ≥ 1.8; Among them [Al + ] 20 [Al] is measured by TOF-SIMS at 20% of the time required for the sputtering gun beam to reach the glass surface. + ] Ion counting; and Among them [Al + ] 80 [Al] is measured by TOF-SIMS at 80% of the time required for the sputtering gun beam to reach the glass surface. + Ion counting.

57. The coated glass element according to claim 56, At least one layer of the coating satisfies the following parameters: [To the + ] 80 / [To the + ] 20 ≥ x1 [Al+] ; Where x1 [Al+] 2.0; and / or [Al + ] 80 / [Al + ] 20 ≤ x2 [Al+] ; Where x2 [Al+] It is 500.

58. The coated glass element according to claim 57, wherein x1 [Al+] For 3; and / or Where x2 [Al+] It is 200.

59. The coated glass element according to claim 57, wherein x1 [Al+] 5; and / or Where x2 [Al+] It is 100.

60. The coated glass element according to claim 57, wherein x1 [Al+] 7; and / or Where x2 [Al+] It is 50.

61. The coated glass element according to claim 57, wherein x1 [Al+] 10; and / or Where x2 [Al+] It is 40.

62. The coated glass element according to claim 57, wherein x1 [Al+] 15; and / or Where x2 [Al+] It is 35.

63. The coated glass element according to claim 57, wherein x1 [Al+] For 20; and / or Where x2 [Al+] It is 30.

64. The coated glass element according to claim 57, wherein x1 [Al+] 25; and / or Where x2 [Al+] It is 29.

65. The coated glass element according to claim 57, wherein x2 [Al+] It is 28.

66. The coated glass element according to any one of claims 56 to 65, The at least one layer comprises the elements Si, O, and C as measured by XPS.

67. The coated glass element according to any one of claims 56 to 65, wherein the thickness of the coating is from 1 nm to 1 mm.

68. The coated glass element according to any one of claims 56 to 65, wherein the thickness of the coating is from 10 nm to 0.5 mm.

69. The coated glass element according to any one of claims 56 to 65, wherein the thickness of the coating is 20 nm to 100 nm.

70. The coated glass element according to any one of claims 56 to 65, The coating is obtained through a single coating process; and / or The coating is in direct contact with the glass surface of the glass element or the glass surface of the pretreated glass element; and / or Wherein at least one layer is the outermost layer; and / or The coating is directed toward the inner cavity of the glass element.

71. The coated glass element according to any one of claims 56 to 65, wherein the coating is a single-layer coating.

72. The coated glass element according to any one of claims 56 to 65, The time required for the sputtering gun beam to reach the glass surface is 0.5 to 60 minutes.

73. The coated glass element of claim 72, wherein the time required for the sputtering gun beam to reach the glass surface is 1 to 10 minutes.

74. The coated glass element of claim 72, wherein the time required for the sputtering gun beam to reach the glass surface is 2 to 4 minutes.

75. A sealed coated glass element, comprising: Coated glass element according to any one of claims 1 to 74; and Closed system.

76. The closed coated glass element of claim 75, wherein the stopper and / or cap is configured as a closure system.

77. A sealed coated glass element, comprising: Coated glass element according to any one of claims 1 to 74; and plunger and / or plunger rod; and / or Closed system.

78. The enclosed coated glass element of claim 77, wherein the tip cap and / or needle shield are configured as an enclosed system.

79. A filled coated glass element, comprising: Coated glass element according to any one of claims 1 to 74; and Composition.

80. The filled coated glass element of claim 79, wherein the composition comprises a pharmaceutical composition.

81. The filled coated glass element according to claim 79, wherein the composition comprises a composition containing a biological product.

82. The filled coated glass element of claim 81, wherein the bioproduct comprises mRNA.

83. A method for producing a coated glass element according to any one of claims 1 to 74, comprising the following steps: - Provide glass components including glass surfaces; and - A coating process is performed on at least a portion of the glass surface, comprising the following steps: a) Enclosing at least a portion of the glass surface of the glass element with the precursor P1; and b) Irradiate the precursor P1 to generate plasma; The following parameters must be satisfied: i) Process temperature PT1 is 320℃ to 500℃; and ii) The irradiation pulse duration PD1 is less than 50 µs.

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